CN102272107A - Pyrimidine derivatives and use thereof for combating undesired plant growth - Google Patents

Pyrimidine derivatives and use thereof for combating undesired plant growth Download PDF

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CN102272107A
CN102272107A CN2009801535241A CN200980153524A CN102272107A CN 102272107 A CN102272107 A CN 102272107A CN 2009801535241 A CN2009801535241 A CN 2009801535241A CN 200980153524 A CN200980153524 A CN 200980153524A CN 102272107 A CN102272107 A CN 102272107A
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alkyl
carbonyl
group
haloalkyl
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CN102272107B (en
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K·迈恩
H·迪特里希
J·迪特根
D·福伊希特
I·豪瑟-哈恩
C·H·罗辛格
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Bayer Intellectual Property GmbH
Bayer CropScience AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/50—Three nitrogen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Compounds of the formula (I) and their use in the field of crop protection are described.

Description

Pyrimidine derivatives and being used to is resisted the purposes of undesired plants growth
The present invention relates to the technical field of crop production compositions, particularly relate to the technical field of the weedicide of the weeds (weed) that are used for selectivity control useful plants crop and weeds (weed grass).
Particularly, the present invention relates to 2-aminopyrimidine, its preparation method and it is used to prevent and treat the purposes of noxious plant.
Prior art discloses the pyrimidine with herbicide effect.For example EP 0 523 533 A1 have described the 4-aminopyrimidine and the purposes in the Crop protection field thereof that replace.WO 2008/043031 discloses as (the R)-6-chloro-N that is used to prepare the intermediate of the purine with pharmacological activity 4-(8-fluoro-chroman-4-yl) pyrimidine-2,4, the 5-triamine.
But, this analog derivative be used for preventing and treating noxious plant as selective herbicide or as plant-growth regulator at the purposes of the multiple beneficial plant crop great rate of application of needs or cause undesirable infringement usually to useful plants.In addition, in many cases, the use of activeconstituents is because high relatively production cost and uneconomical.
Therefore be desirable to provide useful as herbicides or plant-growth regulator and compare instead of chemical activeconstituents with the known system of prior art based on pyrimidine derivatives with some advantage.
Therefore, in general, the purpose of this invention is to provide useful as herbicides or the plant-growth regulator substituting pyrimidine derivatives of---particularly noxious plant is had gratifying weeding activity, noxious plant is had the wide spectrum effect and/or have highly selective in the useful plants crop---.These pyrimidine derivatives are herein compared with pyrimidine derivatives well known in the prior art should preferably demonstrate better character, particularly to the better weeding activity of noxious plant, to the effect of the more wide spectrum of noxious plant and/or in the useful plants crop, have higher selectivity.
And, found to be advantageously used for the new pyrimidines of weedicide and plant-growth regulator according to the present invention.Except that having good active characteristics (profile) and crop plants consistency, the characteristics of this series compound are, preparation method and Yi acquired (access option) cheaply be not because material of the present invention can and thereby can use costliness and the relatively poor intermediate of availability by precursor preparation cheap and easy to get.
Therefore, the invention provides the compound and the salt thereof of formula (I)
Figure BPA00001392541200021
Wherein
R 1And R 2Be independently from each other
-hydrogen, halogen, hydroxyl, cyano group, nitro, amino, C (O) OH, C (O) NH 2
-(C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 1-C 6) alkyl-carbonyl, (C 1-C 6) halogenated alkyl carbonyl, (C 1-C 6) alkyl-carbonyl oxygen base, (C 1-C 6) halogenated alkyl carbonyl oxygen base, (C 1-C 6) alkyl-carbonyl-(C 1-C 4) alkyl;
-(C 1-C 6) alkoxyl group, (C 1-C 6) halogenated alkoxy, (C 1-C 6) alkoxy carbonyl, (C 1-C 6) halo alkoxy carbonyl, (C 1-C 6) alkoxy carbonyl-(C 1-C 6) alkyl, (C 1-C 6) halo alkoxy carbonyl-(C 1-C 6) alkyl, (C 1-C 6) alkoxy carbonyl-(C 1-C 6) haloalkyl, (C 1-C 6) halo alkoxy carbonyl-(C 1-C 6) haloalkyl;
-(C 2-C 6) thiazolinyl, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkenyl carbonyl, (C 2-C 6) haloalkenyl group carbonyl, (C 2-C 6) alkene oxygen base, (C 2-C 6) haloalkene oxygen base, (C 2-C 6) allyloxycarbonyl, (C 2-C 6) the halo allyloxycarbonyl;
-(C 2-C 6) alkynyl, (C 2-C 6) halo alkynyl, (C 2-C 6) alkynyl carbonyl, (C 2-C 6) halo alkynyl carbonyl, (C 2-C 6) alkynyloxy group, (C 2-C 6) halo alkynyloxy group, (C 2-C 6) alkynyloxy group carbonyl, (C 2-C 6) halo alkynyloxy group carbonyl;
-three (C 1-C 6) alkyl silyl-(C 2-C 6) alkynyl, two (C 1-C 6) alkyl silyl-(C 2-C 6) alkynyl, list (C 1-C 6) alkyl silyl-(C 2-C 6) alkynyl, phenyl silyl-(C 2-C 6) alkynyl;
-(C 6-C 14) aryl, (C 6-C 14) aryloxy, (C 6-C 14) aryl carbonyl and (C 6-C 14) aryloxycarbonyl, its aryl moiety separately can be by halogen, (C 1-C 6) alkyl and/or (C 1-C 6) the haloalkyl replacement;
-(C 6-C 14) aryl-(C 1-C 6) alkyl, (C 6-C 14) aryl-(C 1-C 6) alkoxyl group, (C 6-C 14) aryl-(C 1-C 6) alkyl-carbonyl, (C 6-C 14) aryl-(C 1-C 6) alkyl-carbonyl oxygen base, (C 6-C 14) aryl-(C 1-C 6) alkoxy carbonyl, (C 6-C 14) aryl-(C 1-C 6) alkoxy-carbonyl oxy;-single ((C 1-C 6) alkyl) amino, single ((C 1-C 6) haloalkyl) amino, two ((C 1-C 6) alkyl) amino, two ((C 1-C 6) haloalkyl) amino, ((C 1-C 6) alkyl-(C 1-C 6) haloalkyl) amino, N-((C 1-C 6) alkyloyl) amino, N-((C 1-C 6) the haloalkane acyl group) amino, aminocarboxyl-(C 1-C 6) alkyl, two (C 1-C 6) alkyl amino-carbonyl-(C 1-C 6) alkyl;
-single ((C 1-C 6) alkyl) aminocarboxyl, list ((C 1-C 6) haloalkyl) aminocarboxyl, two ((C 1-C 6) alkyl) aminocarboxyl, two ((C 1-C 6) haloalkyl) aminocarboxyl, ((C 1-C 6) alkyl-(C 1-C 6) haloalkyl) aminocarboxyl, N-((C 1-C 6) alkyloyl) aminocarboxyl, N-((C 1-C 6) the haloalkane acyl group) aminocarboxyl;
-(C 1-C 6) alkoxyl group-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group-(C 1-C 6) alkoxyl group, (C 1-C 6) alkoxy carbonyl-(C 1-C 6) alkoxyl group;
-(C 3-C 8) cycloalkyl, its group of naphthene base can be by (C 1-C 6) alkyl and/or the optional replacement of halogen; (C 3-C 8) cycloalkyloxy, (C 3-C 8) cycloalkyl-(C 1-C 6) alkyl, (C 3-C 8) cycloalkyl-(C 1-C 6) haloalkyl, (C 3-C 8) cycloalkyl-(C 1-C 6) alkoxyl group, (C 3-C 8) cycloalkyl-(C 1-C 6) halogenated alkoxy, (C 3-C 8) naphthene base carbonyl, (C 3-C 8) cyclo alkoxy carbonyl, (C 3-C 8) cycloalkyl-(C 1-C 6) alkyl-carbonyl, (C 3-C 8) cycloalkyl-(C 1-C 6) halogenated alkyl carbonyl, (C 3-C 8) cycloalkyl-(C 1-C 6) alkoxy carbonyl, (C 3-C 8) cycloalkyl-(C 1-C 6) halo alkoxy carbonyl, (C 3-C 8) naphthene base carbonyl oxygen base, (C 3-C 8) cyclo alkoxy carbonyl oxygen base, (C 3-C 8) cycloalkyl-(C 1-C 6) alkyl-carbonyl oxygen base, (C 3-C 8) cycloalkyl-(C 1-C 6) halogenated alkyl carbonyl oxygen base, (C 3-C 8) cycloalkyl-(C 1-C 6) alkoxy-carbonyl oxy, (C 3-C 8) cycloalkyl-(C 1-C 6) halo alkoxy carbonyl oxygen base;
-(C 3-C 8) cycloalkenyl group, (C 3-C 8) cyclenes oxygen base, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) haloalkyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkoxyl group, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halogenated alkoxy, (C 3-C 8) cycloalkenyl carbonyl, (C 3-C 8) ring allyloxycarbonyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkyl-carbonyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halogenated alkyl carbonyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkoxy carbonyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halo alkoxy carbonyl, (C 3-C 8) cycloalkenyl carbonyl oxygen base, (C 3-C 8) cyclenes oxygen base ketonic oxygen base, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkyl-carbonyl oxygen base, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halogenated alkyl carbonyl oxygen base, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkoxy-carbonyl oxy, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halo alkoxy carbonyl oxygen base;
-hydroxyl-(C 1-C 6) alkyl, hydroxyl-(C 1-C 6) alkoxyl group, cyano group-(C 1-C 6) alkoxyl group, cyano group-(C 1-C 6) alkyl;
-(C 1-C 6) alkyl sulphonyl, (C 1-C 6) alkylthio, (C 1-C 6) alkyl sulphinyl, (C 1-C 6) halogenated alkyl sulfonyl, (C 1-C 6) halogenated alkylthio, (C 1-C 6) haloalkyl sulfinyl, (C 1-C 6) alkyl sulphonyl-(C 1-C 6) alkyl, (C 1-C 6) alkylthio-(C 1-C 6) alkyl, (C 1-C 6) alkyl sulphinyl-(C 1-C 6) alkyl, (C 1-C 6) halogenated alkyl sulfonyl-(C 1-C 6) alkyl, (C 1-C 6) halogenated alkylthio-(C 1-C 6) alkyl, (C 1-C 6) haloalkyl sulfinyl-(C 1-C 6) alkyl, (C 1-C 6) alkyl sulphonyl-(C 1-C 6) haloalkyl, (C 1-C 6) alkylthio-(C 1-C 6) haloalkyl, (C 1-C 6) alkyl sulphinyl-(C 1-C 6) haloalkyl, (C 1-C 6) halogenated alkyl sulfonyl-(C 1-C 6) haloalkyl, (C 1-C 6) halogenated alkylthio-(C 1-C 6) haloalkyl, (C 1-C 6) haloalkyl sulfinyl-(C 1-C 6) haloalkyl, (C 1-C 6) alkylsulfonyloxy, (C 1-C 6) haloalkyl sulfonyloxy, (C 1-C 6) alkylthio carbonyl, (C 1-C 6) halogenated alkylthio carbonyl, (C 1-C 6) alkylthio ketonic oxygen base, (C 1-C 6) halogenated alkylthio ketonic oxygen base, (C 1-C 6) alkylthio-(C 1-C 6) alkyl, (C 1-C 6) alkylthio-(C 1-C 6) alkoxyl group, (C 1-C 6) alkylthio-(C 1-C 6) alkyl-carbonyl, (C 1-C 6) alkylthio-(C 1-C 6) alkyl-carbonyl oxygen base, (C 4-C 14) aryl sulfonyl, (C 6-C 14) arylthio, (C 6-C 14) aryl sulfonyl kia, (C 3-C 8) cycloalkylthio, (C 3-C 8) alkenylthio group, (C 3-C 8) cyclenes sulfenyl, (C 3-C 6) the alkynes sulfenyl;
-radicals R 1And R 2Form (a C that can contain one or more oxygen and/or sulphur atom together 2-C 6) alkylidene group, wherein said (C 2-C 6) alkylidene group can be replaced by the halogen list or polysubstituted, and each halogenic substituent can be identical or different;
R 3Be selected from hydrogen, (C 1-C 6) alkyl and (C 1-C 6) haloalkyl;
R 4And R 5Be selected from hydrogen, (C independently of one another separately 1-C 6) alkyl, (C 1-C 6) haloalkyl, hydroxyl, (C 1-C 6) alkoxyl group and (C 1-C 6) halogenated alkoxy; Or form 3 to 7 yuan of rings with the carbon atom of their institute's bondings;
R 6And R 7Be selected from hydrogen, (C independently of one another separately 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 1-C 6) alkoxyl group, (C 1-C 6) halogenated alkoxy, (C 6-C 14) aryl, (C 6-C 14) aryloxy, (C 6-C 14) aryl carbonyl and (C 6-C 14) aryloxycarbonyl; Or radicals R 6And R 7Form (a C that can contain one or more oxygen and/or sulphur atom together 2-C 7) alkylidene group, wherein said (C 2-C 7) alkylidene group can be replaced by the halogen list or polysubstituted, and each halogenic substituent can be identical or different;
R 8, R 9, R 10And R 11Be selected from hydrogen, halogen, cyano group, nitro, (C independently of one another separately 1-C 6) alkyl, (C 1-C 6) alkyl-carbonyl, (C 1-C 6) alkoxy carbonyl, (C 1-C 6) alkyl amino-carbonyl, (C 1-C 6) dialkylamino carbonyl, (C 1-C 6) haloalkyl, (C 1-C 6) alkoxyl group, (C 1-C 6) halogenated alkoxy, (C 2-C 6) alkynyl, (C 2-C 6) halo alkynyl, (C 2-C 6) alkynyl carbonyl, (C 2-C 6) halo alkynyl carbonyl, (C 2-C 6) alkynyloxy group, (C 2-C 6) halo alkynyloxy group, (C 2-C 6) alkynyloxy group carbonyl and (C 2-C 6) halo alkynyloxy group carbonyl; And
X is a key, CH 2, O, S, carbonyl, NH, CR 12R 13And NR 14,
R 12And R 13Be selected from hydrogen, (C independently of one another separately 1-C 6) alkyl and (C 1-C 6) haloalkyl,
R 14Be selected from hydrogen, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl,
A) condition is if R 2Be CF 3, R then 1, R 4, R 5, R 6, R 7, R 8, R 9, R 10Or R 11In at least one group be not hydrogen,
B) if R 1Be NH 2, R then 2Be not chlorine.
The difference of the compound among The compounds of this invention and EP 0 523 533A1 is that they are two cyclosubstituted 4-aminopyrimidine-2-amine.
According to the present invention, find that these compounds have good active characteristics and crop plants consistency.
Now, at first each substituent preferred, particularly preferred and extremely particularly preferred implication is described below.
First embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 1Be preferably selected from hydrogen, halogen, cyano group, C (=O) NH 2, NO 2, (C 1-C 6) alkyl, (C 1-C 6) alkyl-carbonyl, (C 1-C 6) haloalkyl, (C 3-C 6) cyclopropyl, (C 1-C 6) alkoxyl group, (C 1-C 6) alkylthio, (C 2-C 6) alkynyl, list (C 1-C 6) alkylamino, two (C 1-C 6) alkylamino and three (C 1-C 6) alkyl silyl-(C 2-C 6) alkynyl;
R 1Be preferably selected from hydrogen, cyano group, fluorine, chlorine, bromine, iodine, nitro, trimethyl silyl ethynyl, methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, n-pentyl, n-heptyl, cyclopropyl, cyclobutyl, ethanoyl, ethynyl, amino, dimethylamino, trifluoromethyl, difluoromethyl, single methyl fluoride, methoxyl group, oxyethyl group and methoxymethyl especially; And
R 1Preferred extremely especially cyano group, ethanoyl or trifluoromethyl.
Second embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 2Be preferably selected from hydrogen, halogen, (C 1-C 6) alkyl phenyl; (C 6-C 14) aryl, its aromatic yl group can be by (C 1-C 6) alkyl, (C 6-C 14) haloalkyl and/or halogen replacement; C 6Aryl-(C 1-C 6) haloalkyl, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 1-C 6) alkoxyl group, (C 1-C 6) alkoxyl group-(C 1-C 6) alkyl; (C 3-C 6) cycloalkyl, its group of naphthene base can be by (C 1-C 6) alkyl, (C 6-C 14) halogenated aryl and/or halogen replacement; 1-(C 1-C 6) alkyl cyclopropyl, 1-((C 1-C 6) alkyl-C 6Aryl) cyclopropyl, 1-(phenyl-monohalide base) cyclopropyl, 1-(dihalogenated phenyl) cyclopropyl, list (C 1-C 6) alkylamino, two (C 1-C 6) alkylamino, (C 1-C 6) alkylthio, (C 1-C 6) alkylthio, (C 1-C 6) alkoxyl group and amino;
R 2Be preferably selected from hydrogen, chlorine, phenyl, 2-aminomethyl phenyl, 3-trifluoromethyl, methyl, ethyl, sec.-propyl, butyl, the tertiary butyl, n-pentyl, n-heptyl, trifluoromethyl, 1-methyl cyclopropyl, 1-(p-Xylol base) cyclopropyl, 1-(2,4 dichloro benzene base) cyclopropyl, amino, dimethylamino, trifluoromethyl, difluoromethyl, single methyl fluoride, CHFCH especially 3, CF (CH 3) 2, CHF (CH 2CH 3), 1-fluorine cyclopropyl, cyclopentyl, methoxyl group, oxyethyl group, methoxymethyl, ethoxyl methyl, sulphomethyl, methylthio group and methoxyl group; And
R 2Preferred extremely especially hydrogen, methyl or difluoromethyl.
Third embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 1And R 2, preferably the carbon atom with their institute's bondings forms one 5 yuan or 6 yuan of rings, and this ring can be selected from 1 or 2 heteroatomss intervals of oxygen and sulphur;
Especially preferably the carbon atom with their institute's bondings forms 5 yuan of rings, and it can be selected from a heteroatoms interval of oxygen and sulphur; And
Extremely especially preferably-CH 2-CH 2-CH 2-or-CH 2-S-CH 2-.
Four embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 3Preferred hydrogen or (C 1-C 6) alkyl; And
R 3Preferred especially hydrogen.
Fifth embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 4And R 5, be preferably selected from hydrogen, (C independently of one another separately 1-C 6) alkyl, hydroxyl, cyclopropyl and (C 1-C 6) alkoxyl group;
R 4And R 5, be preferably selected from hydrogen, methyl, ethyl, propyl group, cyclopropyl, hydroxyl and methoxyl group independently of one another separately especially; And
R 4And R 5, extremely special separately independently of one another preferable methyl, ethyl or hydrogen.
In the 5th embodiment, especially preferred is radicals R 4Or R 5In at least one be hydrogen.Radicals R further preferably 4Or R 5In at least one be hydrogen, and R 4Or R 5In another group be not hydrogen, in particular for (C 1-C 6) alkyl.
In the 5th embodiment, extremely especially preferred is radicals R 4Or R 5One of be hydrogen, and R 4Or R 5In another group be methyl.
Sixth embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 4And R 5Preferably form (a C that can contain one or more oxygen and/or sulphur atom together 2-C 7) alkylidene group, wherein said (C 2-C 7) alkylidene group can be replaced by the halogen list or polysubstituted, and each halogenic substituent can be identical or different; And
R 4And R 5, especially preferably-CH 2-CH 2-CH 2-or-CH 2-CH 2-.
Seventh embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 6And R 7, be preferably selected from hydrogen, (C independently of one another 1-C 6) alkyl and (C 6-C 14) aryl;
R 6And R 7, be preferably selected from hydrogen, methyl and phenyl independently of one another especially; And
R 6And R 7, preferred extremely especially hydrogen.
Eighth embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 8Be preferably selected from hydrogen, (C 1-C 6) alkyl or halogen;
R 8Be preferably selected from hydrogen, methyl or fluorine especially; And
R 8Preferred extremely especially hydrogen.
Ninth embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 9Be preferably selected from hydrogen and (C 1-C 6) alkyl;
R 9Be preferably selected from hydrogen and methyl especially; And
R 9Preferred extremely especially hydrogen.
Tenth embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 10Be preferably selected from hydrogen, (C 1-C 6) alkyl, two (C 1-C 6) alkylamino, halogen, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 1-C 6) alkyl-(C 2-C 6) alkynyl, (C 1-C 6) alkoxyl group-(C 1-C 6) alkyl-(C 2-C 6) alkynyl, cyano group, (C 1-C 6) alkoxy carbonyl and aminocarboxyl;
R 10Be preferably selected from hydrogen, methyl, propyl group, sec.-propyl, butyl, the tertiary butyl, dimethylamino, fluorine, chlorine, bromine, iodine, vinyl, ethynyl, methylacetylenyl, ethylacetylene base, MeOCH especially 2C ≡ C-, cyano group, COOMe and CONH 2And
R 10Preferred extremely especially hydrogen or methyl.
Eleventh embodiment of the invention comprises the compound as shown in the formula (I), wherein
R 11Be preferably selected from hydrogen and (C 1-C 6) alkyl;
R 11Be preferably selected from hydrogen and methyl especially; And
R 11Preferred extremely especially hydrogen.
Twelveth embodiment of the invention comprises the compound as shown in the formula (I), wherein
X is preferably selected from CH 2, O, NH, chemical bond and S; And
X is preferably selected from CH especially 2, O and a chemical bond.
In the present invention, substituent R 1To R 11And each preferred, particularly preferred and extremely particularly preferred implication of X can be bonded to each other on demand.This compound that means this shape includes within the scope of the present invention, for example substituent R wherein 1Have preferred implication and substituent R 2To R 11Have wide in range implication, or substituent R 2Have preferred implication, substituent R 3Has particularly preferred implication and all the other substituting groups have wide in range implication.
In the present invention, formula (I) compound also comprises by carry out a) protonated, b on nitrogen-atoms) alkylation or c) oxidation and by quaternised compound.
Formula (I) compound can form salt.
Salt can form by those formulas (I) compound that alkali is acted on have acid hydrogen atom, for example works as R 1Contain a COOH base or sulfonamido-NHSO 2-time and forming.Suitable alkali for example has: organic amine (for example trialkylamine), morpholine, piperidines or pyridine; And the oxyhydroxide of ammonium, basic metal or alkaline-earth metal, carbonate and supercarbonate, particularly sodium hydroxide and potassium hydroxide, yellow soda ash and salt of wormwood, and sodium bicarbonate and saleratus.These salt are that wherein acidic hydrogen is applied to agriculture positively charged ion alternate compound, for example: metal-salt, particularly an alkali metal salt or alkaline earth salt, particularly sodium salt and sylvite; And ammonium salt, with the salt or the quaternary ammonium salt of organic amine, it for example has formula [NRR ' R " R " '] +Positively charged ion, R to R in the formula " ' be organic group, particularly alkyl, aryl, aralkyl or alkaryl separately independently of one another.Also suitable have alkyl sulfonium salt and alkyl oxidation sulfonium salt, for example (a C 1-C 4) triakylsulfonium salts and (C 1-C 4) trialkyl oxidation sulfonium salt.
Formula (I) compound can carry out addition reaction by suitable inorganic or organic acid and basic group (for example amino, alkylamino, dialkylamino, piperidino-(1-position only), morpholino or pyrido) and form salt, for example mineral substance acid of described mineral acid (mineral acid) is as HCl, HBr, H 2SO 4, H 3PO 4Or HNO 3, described organic acid is carboxylic acid (as formic acid, acetate, propionic acid, oxalic acid, lactic acid or Whitfield's ointment) or sulfonic acid (as tosic acid) for example.Thereby make these salt contain the conjugate base of described acid as negatively charged ion.
The suitable substituting group (for example sulfonic acid or carboxylic acid) that exists with the deprotonation form can with protonated group (for example amino) can take place itself forms inner salt.
Formula of the present invention or used according to the invention (I) compound and salt thereof also are called " compound (I) " hereinafter for short.
In formula (I) and all other formulas of the present invention, the group alkyl in the carbon backbone chain, alkoxyl group, haloalkyl, halogenated alkoxy, alkylamino, alkylthio, halogenated alkylthio and corresponding group undersaturated and/or that replace can respectively do for oneself straight chain or side chain.Indicate unless have clearly, otherwise for these groups, preferred rudimentary carbon backbone chain for example has the rudimentary carbon backbone chain of 1-6 carbon atom, a particularly 1-4 carbon atom, or has the rudimentary carbon backbone chain of 2-6 carbon atom, a particularly 2-4 carbon atom under the situation of unsaturated group.Alkyl group, be included in the alkyl group in the compound implication (for example alkoxyl group, haloalkyl etc.), for example mean methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl or 2-butyl, amyl group, hexyl (for example n-hexyl, isohexyl and 1, the 3-dimethylbutyl), heptyl (for example n-heptyl, 1-methyl hexyl and 1,4-dimethyl amyl group); The implication that thiazolinyl and alkynyl group have is and the corresponding possible unsaturated group of described alkyl group wherein to have at least one two keys or triple bond, preferred two keys or triple bond.Thiazolinyl has for example vinyl, allyl group, 1-methyl-prop-2-alkene-1-base, 2-methyl-prop-2-alkene-1-base, but-2-ene-1-base, fourth-3-alkene-1-base, 1-methyl fourth-3-alkene-1-base and 1-methyl but-2-ene-1-base; Alkynyl has for example ethynyl, propargyl, fourth-2-alkynes-1-base, fourth-3-alkynes-1-base and 1-methyl fourth-3-alkynes-1-base.
Cycloalkyl has for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.Described cycloalkyl can dicyclo or the existence of trinucleated form.
If provided the halogenated alkyl group in halogenated alkyl group and halogenated alkoxy, halogenated alkylthio, haloalkenyl group, the halo alkynyl etc., then in these groups in rudimentary carbon backbone chain (for example having 1-6 carbon atom or 2-6, particularly 1-4 carbon atom or preferred 2-4 carbon atom) and the described carbon backbone chain group undersaturated accordingly and/or replacement respectively do for oneself straight chain or side chain.Example has difluoromethyl, 2,2,2-trifluoroethyl, trifluoro allyl group, 1-chlorine third-1-base-3-base.
In these groups, alkylidene group is the group of corresponding undersaturated and/or replacement in rudimentary carbon backbone chain (for example have 1-10 carbon atom, a particularly 1-6 carbon atom or preferred 2-4 carbon atom) and the described carbon backbone chain, and is that it can be straight chain separately or side chain.Example has methylene radical, ethylidene, positive propylidene and isopropylidene, reaches positive butylidene, sec.-butylidene, isobutylene, uncle's butylidene.
In these groups, hydroxyalkyl group is the corresponding undersaturated and/or group that replaces in rudimentary carbon backbone chain (for example having 1-6 carbon atom, a particularly 1-4 carbon atom) and the described carbon backbone chain, and is that it can be straight chain separately or side chain.The example has 1,2-dihydroxy ethyl and 3-hydroxypropyl.
Halogen is fluorine, chlorine, bromine or iodine.Haloalkyl, haloalkenyl group and halo alkynyl are respectively by halogen---preferably by fluorine, chlorine or bromine, particularly by fluorine and/or chlorine---and alkyl, alkenyl or alkynyl that part replaces or all replaces, for example a haloalkyl, whole haloalkyl, CF 3, CHF 2, CH 2F, CF 3CF 2, CH 2FCHCl, CCl 3, CHCl 2, CH 2CH 2Cl; Halogenated alkoxy has for example OCF 3, OCHF 2, OCH 2F, CF 3CF 2O, OCH 2CF 3And OCH 2CH 2Cl; This is applicable to haloalkenyl group and other group that is replaced by halogen with shape.
Aryl is monocycle, dicyclo or polycyclic aromatic system, for example phenyl or naphthyl, preferably phenyl.
Mainly due to having higher weeding activity, better selectivity and/or better preparation property, therefore formula of the present invention (I) compound or its agrochemistry salt or season N derivative are concerned by people especially, wherein each group has indicated or one of indicated preferred meaning hereinafter, or in the particularly described group one or more indicated or hereinafter indicated preferred meaning in conjunction with exist those.
Above wide in range or both be applicable to the group definition that preferable range provides that formula (I) end product also correspondingly was applicable to required raw material and the intermediate of preparation under every kind of situation.These group definition can be exchanged each other and between described its preferable range.
Formula of the present invention (I) compound has at the following chiral carbon atom that is illustrated by symbol (*) in the structure of painting:
According to Cahn, Ingold and Prelog rule (CIP rule), this carbon atom can have (R) configuration or (S) configuration.
The present invention had both comprised that having (S) configuration also comprised formula (I) compound with (R) configuration, promptly the present invention includes the compound as shown in the formula (I), and wherein said carbon atom has
(1) (R) configuration; Or
(2) (S) configuration.
In addition, the present invention also comprises
(3) formula (I) compound (compound of formula (I-(R))) and any required mixture that have (R) configuration with formula (I) compound (compound of formula (I-(S))) of (S) configuration.
Wherein have (R) configuration and (S) racemic mixture of the formula of configuration (I) compound be also included within the scope of the invention.
But, in the present invention, formula (I) compound of (R) configuration that especially preferably having selectivity is 60-100%---preferred 80-100%, particularly 90-100%, the utmost point be 95-100% particularly---, wherein the enantioselectivity of concrete (R) compound of Cun Zaiing is separately greater than 50%ee, preferred 60-100%ee, particularly 80-100%ee, the utmost point particularly 90-100%ee, 95-100%ee most preferably, and each value is all based on the total content meter of described (R) compound.
Therefore, The present invention be more particularly directed to the compound as shown in the formula (I), wherein the stereochemistry purity of the three-dimensional chemical configuration that exists on the carbon atom that is indicated by (*) is particularly 95-100% (R) of 60-100% (R), preferred 80-100% (R), particularly 90-100% (R), the utmost point.
Consider Cahn, Ingold and Prelog rule, on the carbon atom that is indicated by (*), because each substituent priority, a kind of situation that also may occur is that wherein the carbon atom that is indicated by (*) is preferably (S) configuration.For example, work as radicals R 4And/or R 5Be C 1-C 6During alkoxy base, belong to this situation.
Therefore, in the present invention, formula (I) compound of preferred especially this shape, its on spatial disposition corresponding to wherein R with (R) configuration 4And R 5Those formulas (I) compound of=hydrogen, the selectivity of described compound is particularly 95-100% of 60-100%, preferred 80-100%, particularly 90-100%, the utmost point, wherein the enantioselectivity of concrete (the R)-similar compound of Cun Zaiing is separately greater than 50%ee, preferred 60-100%ee, particularly 80-100%ee, the utmost point particularly 90-100%ee, 95-100%ee most preferably, and each value is all based on the total content meter of described (R)-similar compound.Therefore, The present invention be more particularly directed to formula (I) compound of this shape, the stereochemistry purity of the three-dimensional chemical configuration of the wherein existing carbon atom that is indicated by (*) is 60-100% (R, or R analogue), preferred 80-100% (R, or R analogue), 90-100% (R particularly, or R analogue), utmost point 95-100% (R, or R analogue) particularly.
Particularly, formula of the present invention (I) compound also can have other chiral centre carbon atoms that indicated by (* *) and (* * *):
Figure BPA00001392541200121
In the present invention, the carbon atom that is indicated by (*), (* *) and (* * *) can have any required three-dimensional chemical configuration:
The configuration of carbon atom (*) The configuration of carbon atom (* *) The configuration of carbon atom (* * *)
R R R
R R S
R S R
S R R
R S S
S R S
S S R
S S S
In addition, according to the selectivity of concrete group, also can there be other three-dimensional elements (stereoelement) in formula of the present invention (I) compound.
For example, if there are one or more alkenyl groups, then can there be diastereomer (Z and E isomer).
For example, if there are one or more unsymmetrical carbons, then can there be enantiomer and diastereomer.
Corresponding steric isomer can be obtained by conventional separation method (for example chromatography) by mixture prepared in the preparation process.Steric isomer also can use the optionally preparation by implementing the stereoselectivity reaction of optically-active raw material and/or auxiliary agent.Therefore the invention still further relates to all steric isomers of that formula (I) is contained but undeclared its concrete three-dimensional form and composition thereof.
Each substituting group bonded possibility of formula (I) is interpreted as, and observes the rule that makes up chemical compound, and promptly formula (I) does not comprise chemically impossible compound well known by persons skilled in the art.
Following table has provided the specific examples of formula of the present invention (I) compound:
Figure BPA00001392541200141
Figure BPA00001392541200171
Figure BPA00001392541200181
Figure BPA00001392541200191
Figure BPA00001392541200201
Figure BPA00001392541200211
Figure BPA00001392541200221
Figure BPA00001392541200231
Figure BPA00001392541200241
Figure BPA00001392541200251
Figure BPA00001392541200261
The present invention also provides the method for the compatible quaternized azepine derivatives of preparation corresponding formula (I) compound and/or its salt and/or its agrochemistry:
A.) be preparation formula (I) compound,
Figure BPA00001392541200271
Radicals R wherein 1To R 11Reach X and have above-mentioned implication,
The compound that can be by making formula (II) and the amine of a kind of formula (III) or its acid salt react and obtain,
Figure BPA00001392541200272
R wherein 1And R 2Have above-mentioned implication, and Z 1Be commutative group or leavings group, for example particularly chlorine, trichloromethyl, (C 1-C 4) alkyl sulphonyl, unsubstituted or phenyl-(C of replacing 1-C 4) alkyl sulphonyl or (C 1-C 4) the alkyl phenyl alkylsulfonyl
Figure BPA00001392541200273
Radicals R wherein 3To R 11And X has above-mentioned implication.
The formula of Z=chlorine (II) compound can obtain by formula (IV) compound and ammonia are reacted by following reaction scheme:
Figure BPA00001392541200281
The isomer mixture of gained (II) and (V) can separate or is used in the subsequent reactions with the form of mixture by chromatography.
The amine of formula (III) or its acid salt is commercially available gets, and it synthesizes in WO 2004/069814A1 description is arranged.
Commercially available the getting of pyrimidine of formula (II), its concrete derivative can be prepared by currently known methods.For example,
A. corresponding 4-hydroxy pyrimidine can be according to Perez et al., Synthesis 1983, disclosure in the 402nd page can transform an accepted way of doing sth (II) compound with its (for example using phosphoryl chloride) then by malonamide nitrile and N-cyano group carboxylic imide acid esters (N-cyanocarboximidoate) preparation;
B.4-hydroxy pyrimidine can be by acetylacetic ester according to Gershon et al., J.Heterocyclic Chem., and 20,219 (1983) and J.Heterocycl.Chem., 21 (4), (1984), disclosed method preparation in 1161, and be translated into chloropyrimide.
B.) be preparation formula (I) compound, compound as described belowly can be changed into other compound of the present invention as precursor and with it:
I. for example, R wherein 1, R 2Or R 10Formula (I) derivative of=halogen (particularly iodine or bromine); can with acetylene or the acetylene that is subjected to trimethyl silyl protection under transition metal-catalyzed (for example using two (triphenylphosphine) palladium chloride (II) catalysis) in protonic solvent or aprotic solvent and add a kind of alkali and under 20-150 ℃ of temperature, react, obtain wherein R 1, R 2Or R 10The formula of=alkynyl (I) compound.
Ii. for example, R wherein 1The formula of=CN (I) derivative carries out saponification under acidity or base catalysis; The carboxylic acid that obtains in this mode can change into chloride of acid by currently known methods, itself then can change into acid amides.
Iii. for example, R wherein 2The formula of=halogen (I) derivative can and add a kind of alkali in protonic solvent or aprotic solvent and transform by reacting with alcoholate or amine under 100-250 ℃ of temperature, obtains wherein R 2The formula of=alkoxyalkyl or aminoalkyl group or Diaminoalkyl (I) compound.
Can also can the parallel mode preparation by the set (collection) of above-mentioned reaction synthetic formula (I) compound and/or its salt, described preparation can be manually, part automatically or fully automatic mode carry out.Thus, can for example implement the purifying of operation, aftertreatment or product and/or intermediate automatically.In a word, this for example is interpreted as meaning by D.Tiebes at Combinatorial Chemistry-Synthesis, Analysis, Screening (editor G ü nther Jung), Verlag Wiley 1999, the operation described in the 1-34 page or leaf.
For parallel operation and aftertreatment, can use a series of commercially available instruments that get, for example available from Barnstead International, Dubuque, Iowa 52004-0797, the Calpyso reaction block of USA (reaction block) or available from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, the reaction station of England (reaction station) or available from Perkin Elmer, Waltham, Massachusetts 02451, the automatic workstation of the multiprobe of USA (MultiPROBE Automated Workstation).For the parallel purification of formula (I) compound and its salt or the intermediate that in preparation process, generates, for example particularly can use available from ISCO Inc., 4700 Superior Street, Lincoln, NE68504, the chromatogram arrangement of USA.
Institute's array apparatus causes the module operation of this shape, and wherein each operation steps is carried out automatically, but must carry out manual operation between each operation steps.This can evade by the automatic system of using sectoral integration or fully integratedization, and wherein each automatization module is for example by the robot manipulation.Such automatic system can be for example from Caliper, Hopkinton, and MA 01748, and USA obtains.
Enforcements single or several synthesis steps can come auxiliary by the reagent/removing resin (scavenger resin) that uses the polymkeric substance load.Technical literature has been described a series of testing programs, for example at ChemFiles, and Vol.4, No.1 is among the Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).
Except that the method that the present invention describes, the preparation of formula (I) compound and salt thereof can completely or partially realize by the solid supported method.For this reason, with described synthetic in or be applicable to that each single intermediate or all intermediates in corresponding operating a certain synthetic are bonded to synthetic resins.The solid supported synthesis method has obtained abundant description in technical literature, for example Barry A.Bunin is in " The Combinatorial Index ", Verlag Academic Press, 1998 and Combinatorial Chemistry-Synthesis, Analysis, Screening (editor G ü nther Jung), Verlag Wiley has carried out abundant description in 1999.Use the solid supported synthesis method can implement known a series of schemes in the document, described scheme also can manually be carried out or carry out in the automatization mode.For example, reaction can be available from Nexus Biosystems, 12140 Community Road, and Poway, CA92064 is undertaken by the IRORI technology in the microreactor of USA.
Carrying out single or several synthesis steps on solid phase and in the liquid phase can be auxiliary by using microwave technology.Technical literature, Microwaves in Organic and Medicinal Chemistry (editor C.O.Kappe and A.Stadler) for example, Verlag Wiley in 2005, has described a series of testing programs.
The preparation that the method for describing in according to the present invention is carried out can obtain formula (I) compound and salt thereof into material set form, is called storehouse (libraries).The present invention also provides the storehouse that comprises at least two kinds of formulas (I) compound and salt thereof.
Because formula (I) compound has herbicidal performance, the present invention also provides formula of the present invention (I) compound is used to prevent and treat noxious plant as weedicide purposes in addition.
In a plurality of cultivation phase process, weedicide is used in the crop that utilizes on the agricultural.For example, some products use in addition the sowing before or carry out between sowing time.Other products are before crop plants is emerged, and---being that seedling gets out before the soil surface---uses (herbicide before seedling stage).At last, if crop plants has formed cotyledon or trophophyll, then use herbicide after seedling.
Herein, The compounds of this invention can be before seedling or postemergence application, and preferred The compounds of this invention is at preemergence application.
The seedling pre-treatment is included in sowing before to the processing (the ppi=kind is mixed before planting) of cultural area, also comprises not growing the processing of sowing cultural area of any grower as yet.
Formula of the present invention (I) compound and salt thereof (same free burial ground for the destitute hereinafter also is called formula (I) compound together) have good herbicide action to the important economically unifacial leaf and the dicotyledonous harmful plants of wide spectrum.Described activeconstituents also can effectively be prevented and treated the perennial weeds that is difficult to prevent and treat that is grown up to by rhizome, root stock or other perennating organs.Herein, this material is still used unimportant to sow preceding method, Miao Qianfa with Miao Houfa.
Especially, the example that can mention is the representational unifacial leaf that can be prevented and treated by formula of the present invention (I) compound and some in the broadleaf weed flora, but describedly enumerates and be not intended to be limited to some species.
To the monocotyledon weed species, Agrostis (Agrostis) for example, amur foxtail belongs to (Alopecurus), Apera, Avena (Avena), Brachiaria (Brachiaria), Brome (Bromus), talon eria (Dactyloctenium), knotgrass (Digitaria), Echinochloa (Echinochloa), Eleocharis (Eleocharis), yard grass belongs to (Eleusine), festuca (Festuca), genus fimbristylis (Fimbristylis), ischaemum (Ischaemum), lolium (Lolium), Monochoria (Monochoria), Panicum (Panicum), Paspalum (Paspalum), phalaris arundinacea (Phalaris), ladder forage spp (Phleum), annual bluegrass belongs to (Poa), arrowhead belongs to (Sagittaria), Scirpus (Scirpus), setaria (Setaria), cusp Pittosporum (Sphenoclea) mainly is annual Cyperus (Cyperus) species; And perennial species Agropyron (Agropyron), Cynodon (Cynodon), cogon (Imperata) and sorghum (Sorghum) and perennial Cyperus species, all can effectively prevent and treat.
For the broadleaf weed species, action spectrum extends to: the galium (Galium) in for example annual species, Viola (Viola), Veronica (Veronica), lamium (Lamium), Stellaria (Stellaria), Amaranthus (Amaranthus), sinapsis alba belong to (Sinapis), Ipomoea (Ipomoea), Matricaria (Matricaria), hemp genus (Abutilon) and chrysanthemum harvest spp (Sida), and the japanese bearbind in the perennial weeds belongs to (Convolvulus), Cirsium (Cirsium), Rumex (Rumex) and artemisia (Artemisia).In addition, to broadleaf weed, Ambrosia (Ambrosia) for example, Anthemis (Anthemis), bristlethistle (Carduus), bachelor's-button (Centaurea), Chenopodium (Chenopodium), Cirsium (Cirsium), japanese bearbind belongs to (Convolvulus), Datura (Datura), thorn Rumex (Emex), the weasel hemp nettle belongs to (Galeopsis), ox achyranthes chrysanthemum spp (Galinsoga), separate row Vegetable spp (Lepidium), Vandellia (Lindernia), papaver (Papaver), Portulaca (Portlaca), Polygonum (Polygonum), Ranunculus (Ranunculus), fall Lepidium (Rorippa), joint joint Lepidium (Rotala), Senecio (Seneceio), Daubentonia (Sesbania), Solanum (Solanum), sonchus L (Sonchus), Dandelion (Taraxacum), Clover (Trifolium), Urtica (Urtica) and Xanthium (Xanthium) also can be observed herbicide effect.
If formula of the present invention (I) compound is applied to soil surface before rudiment, can prevent fully that then weeds from coming up, perhaps weed growth reaches cotyledon period to it, but its growth stops subsequently, and finally three to around the back thoroughly dead.
If with the activeconstituents of formula (I) at postemergence application during in the green plant position, the utmost point after processing is grown in the short period of time and is sharply stopped with shape, and the growth phase when ruderal plant rests on described using, or it is thoroughly dead after the certain hour section, thereby can the utmost point early and in persistent mode eliminates by to the deleterious weed competition of crop plants in this mode.
Though formula of the present invention (I) compound has excellent herbicidal to unifacial leaf and broadleaf weed, but to the crop plants of important crop economically, for example, wheat, barley, rye, rice, corn, beet, cotton, rape and soybean, only has the infringement that to ignore degree, if there is infringement.Therefore, the high degree of The compounds of this invention is suitable for undesired plant-growth in the upward useful kind of plant of selectivity control agricultural.
In addition, formula of the present invention (I) material has good growth regulating performance to crop plants.They intervene the metabolism of plant with control methods, and thereby can be used for directedly influence plant constituent and being convenient to gather, for example dewater and stunted growth by causing.In addition, they also are suitable for control usually and suppress undesired and nourish and grow, and can not damage plant in this process.Suppressing nourishes and grows all plays very big effect to many unifacial leaves and dicotyledonous crops, can reduce or prevent fully to lodge.
Described activeconstituents is because it has weeding and plant growth regulating performance, therefore also can be used for preventing and treating the known plants crop or the genetically modified plant crop that waits to develop in noxious plant.Generally speaking, transgenic plant are celebrated with specific favorable properties, for example---as some insect or microorganism (as fungi, bacterium or virus)---has resistance so that some agricultural chemicals (mainly being some weedicide) is had resistance, to Plant diseases or Plant diseases pathogenic agent.Other special character relate to, for example the quantity of harvested material, quality, storage, composition and concrete composition.Therefore, known transgenic plant have the starch content or the improved starch quality of increase, or its harvested material has different lipid acid compositions.Other special character can be, abiotic stress factor (for example hot, cold, arid, salt and uv-radiation) is had tolerance or resistance.
Preferably formula of the present invention (I) compound or its salt is used for important economically useful plants and the genetically modified crops of ornamental plant, described crop is cereal such as wheat, barley, rye, oat, broomcorn millet, rice, cassava and corn or other crop beets, cotton, soybean, rape, potato, tomato, pea and other vegetable varieties for example.
Preferably, formula (I) compound can be used as weedicide and is used in phytotoxicity effect to weedicide and has resistance or it has been had in the useful plants crop of genetic resistance.
The ordinary method with the new plant that improves performance is compared in generation to be had with existing plant, for example conventional cultural method and generation mutant.Perhaps, can use gene engineering method to produce to have the new plant that improves performance (referring to, for example EP 0221044, EP 0131624).Following several situations have for example been described:
A) crop plants is carried out genetic modification with synthetic starch (for example WO 92/011376, WO 92/014827, WO 91/019806) in the change plant,
B) to careless ammonium phosphine (glufosinate) class (referring to for example, EP 0242236, EP 0242246) or genetically modified crops plant with resistance of some weedicide of glyphosate (glyphosate) class (WO 92/000377) or sulfonylurea (EP 0257993, US 5013659)
C) can produce bacillus thuringiensis toxin (Bacillus thuringiensis toxin, Bt toxin) thus the genetically modified crops plant that makes plant have resistance to some insect, cotton (EP 0142924, EP 0193259) for example,
D) have the genetically modified crops plant (WO 91/013972) that the lipid acid of change is formed,
E) have the genetic modification crop plants (EP 0309862, EP 0464461) of new composition or secondary substance (secondary substance) (for example new phytoalexin, it improves disease resistance),
F) genetically modified plant of photorespiration reduction, it has higher productive rate and the stress tolerance of Geng Gao (EP 0305398),
G) produce in the pharmacy or genetically modified crops plant (" the molecule medicine is ploughed (molecular pharming) ") that important protein matter is gone up in diagnosis,
H) the higher or better genetically modified crops plant that is celebrated of quality with productive rate,
I) the genetically modified crops plant that is celebrated with the combination of for example above-mentioned new features (" gene stack (gene stacking) ").
Can be used for producing the many molecular biotechnologies with the new transgenic plant that changes characteristic is known in principle; Referring to for example I.Potrykus and G.Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg or Christou, " Trends in Plant Science " 1 (1996) 423-431.
In order to carry out this type of genetic manipulation, can will be able to introduce in the plasmid by the nucleic acid molecule that the dna sequence dna reorganization is undergone mutation or sequence changes.For example, can implement base substitution, remove subsequence or add natural or composition sequence by standard method.For dna fragmentation is connected to each other, can add adapter or linker to fragment, referring to, people such as Sambrook for example, 1989, Molecular Cloning, A Laboratory Manual, the 2nd edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; Or Winnacker " Gene und Klone[Genes and Clones] ", VCH Weinheim the 2nd edition 1996.
The active vegetable cell that reduces of gene product can be for example by expressing at least a corresponding sense-rna, being used for realizing inhibiting just RNA altogether, and perhaps the ribozyme of the corresponding structure of the transcript by expressing at least a specificity cracking said gene product generates.For this reason, can at first use the dna molecular of the entire coded sequence (comprising any flanking sequence that may exist) that comprises gene product, and use the dna molecular that only comprises the part encoding sequence, these parts need sufficiently long so that produce antisense effect in cell.Can also use the encoding sequence with gene product to have high homology but not identical with it dna sequence dna.In the express nucleic acid molecular process, synthetic protein can be positioned in any compartment of vegetable cell in plant.But, can for example make coding region and guarantee that localized dna sequence dna links to each other in specific compartment for being implemented in the location in the specific compartment.This type of sequence is that well known by persons skilled in the art (referring to, people such as Braun for example, EMBO is (1992) J.11,3219-3227; People such as Wolter, Proc.Natl.Acad.Sci.USA 85 (1988), 846-850; People such as Sonnewald, Plant be (1991) J.1,95-106).Nucleic acid molecule also can be expressed in the organoid of vegetable cell.
Thereby transgenic plant cells can obtain complete plant by known technology regeneration.In principle, transgenic plant can be the plants of any required plant species, promptly both can be monocotyledons and also can be dicotyledons.
Therefore, having the transgenic plant that change characteristic can express, prevent or suppress homology (=natural) gene or gene order by crossing, or expressing heterologous (=external source) gene or gene order and obtain.
Formula of the present invention (I) compound can preferably be used in to have in the genetically modified crops of resistance following material: growth regulator, for example dicamba 98 (dicamba); Or the weedicide of the essential plant enzyme of inhibition, described enzyme is acetolactate synthase (ALS), EPSP synthase, glutamine synthetase (GS) or hydroxyphenylpyruvate dioxygenase (HPPD) for example; Or be selected from the weedicide of sulfonylurea, glyphosate, careless ammonium phosphine or benzoyl isooxazole and similar activeconstituents.
When with formula of the present invention (I) when activeconstituents is used for genetically modified crops, except can be in other crops the observed effect to noxious plant, specific effect when being applied to specific genetically modified crops, also often occurs, for example changed or particularly widened the weeds spectrum that to prevent and treat, changed spendable rate of application when using, preferably it had the good combination of weedicide of resistance and growth and the productive rate that influences the genetically modified crops plant with genetically modified crops.
Therefore, the present invention also provides formula of the present invention (I) compound is used for preventing and treating genetically modified crops plant noxious plant as weedicide purposes.
Formula (I) compound can be prepared in many ways according to specified biology and/or the physical-chemical parameters.Dosage forms for example has: spraying pulvis (WP), water solube powder (SP), water-soluble enriching agent, missible oil (EC), emulsion (EW) (as oil-in-water emulsion and water-in-oil emulsion), the sprayable solution agent, suspension concentrate (SC), oil base or water base dispersion agent, solution that can be miscible with oil, capsule suspension (CS), dusting powder (DP), seed dressing, broadcast sowing and soil is executed granule, particulate, the spraying granule agent, the granule (GR) of coated granule and absorbability particle agent form, water-dispersible granules (WG), water-soluble granular formulation (SG), the ULV preparation, microcapsule and cerate.
These various types of preparations are known in principle, and for example describing to some extent in the following document: Winnacker-K ü chler, " Chemische Technologie[Chemical Technology] ", volume 7, C.Hanser Verlag Munich, the 4th edition 1986; Wade van Valkenburg, " Pesticide Formulations ", Marcel Dekker, N.Y., 1973; K.Martens, " Spray Drying " Handbook, the 3rd edition 1979, G.Goodwin Ltd.London.
Required formulation aid (for example inert substance, tensio-active agent, solvent and other additives) also is known, and for example in the following document description: Watkins is being arranged, " Handbook of Insecticide Dust Diluents and Carriers ", the 2nd edition, Darland Books; Caldwell N.J., H.v.Olphen, " Introduction to Clay Colloid Chemistry ", the 2nd edition, J.Wiley﹠amp; Sons, N.Y.; C.Marsden, " Solvents Guide ", the 2nd edition, Interscience, N.Y.1963; " the Detergents and Emulsifiers Annual " of McCutcheon, MC Publ.Corp., Ridgewood N.J.; Sisley and Wood, " Encyclopedia of Surface Active Agents ", Chem.Publ.Co.Inc., N.Y.1964; " [Surface-active ethylene oxide adducts] ", Wiss.Verlagsgesell., Stuttgart 1976; Winnacker-K ü chler, " Chemische Technologie[Chemical Technology] ", volume 7, C.Hanser Verlag Munich, the 4th edition, 1986.
---for example promptly mixing thing or the mixed thing form of the bucket---binding substances that on the basis of these preparations, also can prepare itself and other pesticidal active substance (for example insecticide, miticide, weedicide, sterilant) and with safener, fertilizer and/or growth regulator.
The spraying pulvis is the preparation that can be dispersed in the water and also contain ion and/or nonionic surface active agent (wetting agent, dispersion agent) except that activeconstituents, except that thinner or inert substance; described tensio-active agent is polyoxyethylated alkylphenol, polyoxy ethylization Fatty Alcohol(C12-C14 and C12-C18), polyoxy ethylization aliphatic amide, fatty alcohol polyglycol ether vitriol, alkyl sulfonate, alkylbenzene sulfonate, sodium lignosulfonate, 2 for example; 2 '-dinaphthyl methane-6; 6 '-sodium disulfonate, sodium dibutyl naphthalene sulfonate, and oleoyl N-methyltaurine sodium.For preparing described spraying pulvis, herbicidal active component is carried out fine grinding in for example conventional equipment (as hammer mill, blowing-type shredder and blast injection shredder), and simultaneously or mix with formulation aid afterwards.
Missible oil is by being dissolved in activeconstituents in the organic solvent and adding one or more ions and/or nonionic surface active agent (emulsifying agent) prepares, and described organic solvent is the mixture of butanols, pimelinketone, dimethyl formamide, dimethylbenzene or high boiling point aromatic substance or hydrocarbon or organic solvent for example.Spendable emulsifying agent for example has: alkyl aryl sulphonic acid calcium salt, for example calcium dodecylbenzene sulphonate; Or nonionic emulsifier, for example condensation product of fatty acid polyglycol ester, alkylaryl polyglycol ether, fatty alcohol polyglycol ether, propylene oxide-oxyethane, alkyl, polyether, sorbitan esters (for example sorbitan fatty(acid)ester) or polyoxyethylene sorbitan esters (for example polyoxyethylene sorbitan fatty acid ester).
Powder agent obtains by activeconstituents is ground with the fine-grained solids material, and described solid matter is talcum, natural clay (as kaolin, wilkinite or pyrophyllite) or diatomite for example.
Suspension concentrate can be water base or oil base.If they can be for example by carrying out wet grinding and prepare---for example hereinbefore at the cited tensio-active agent of other types preparation---by standard available sand mill and suitable interpolation tensio-active agent together.
Emulsion, oil-in-water emulsion (EW) for example is if can for example use aqueous organic solvent and suitable surfactant---for example hereinbefore at the cited tensio-active agent of other types preparation---to prepare by agitator, colloidal mill and/or static mixer together.
Granule can prepare by activeconstituents being atomised on the particulate inert material that can adsorb, or by by tackiness agent (for example polyvinyl alcohol, sodium polyacrylate or mineral oil) active ingredient concentrate being applied to carrier substance (for example sand, kaolin) or the surface of particulate inert material prepares.The usual manner that suitable activeconstituents also can prepare fertiliser granulates---mixes mutually with fertilizer if desired---and makes particle.
Water-dispersible granules is usually by the ordinary method preparation, and described ordinary method for example spraying drying, fluidized bed prilling, disk granulation (pan granulation), super mixer is mixed and extruded under the situation of no solid, inert material.
For disk granulation, fluidized bed prilling, forcing machine granulation and mist projection granulating, referring to the method in the following document for example: " Spray-Drying Handbook " the 3rd edition 1979, G.Goodwin Ltd., London; J.E.Browning, " Agglomeration ", 1967, the 147 pages of Chemical and Engineering and after; " Perry ' s Chemical Engineer ' s Handbook ", the 5th edition, McGraw-Hill, New York 1973, the 8-57 pages or leaves.
Other detailed contents of relevant crop production compositions preparation, referring to for example G.C.Klingman, " Weed Control as a Science "; John Wiley and Sons, Inc., New York; 1961,81-96 page or leaf and J.D.Freyer, S.A.Evans; " Weed Control Handbook "; the 5th edition, Blackwell Scientific Publications, Oxford; 1968, the 101-103 page or leaf.
Agrochemical formulations contains 0.1-99 weight %, the particularly formula of 0.1-95 weight % (I) activeconstituents usually.
In the spraying pulvis, activity component concentration is for example about 10-90 weight %, is made of the conventional formulation component to the surplus thing of 100 weight %.Under the situation of missible oil, activity component concentration can be about 1-90 weight %, preferred 5-80 weight %.Powder preparation contains the activeconstituents of 1-30 weight %, the activeconstituents of preferred 5-20 weight % in most of the cases, and sprayable solution contains the activeconstituents of the 0.05-80 weight % that has an appointment, preferred 2-50 weight %.Under the situation of water-dispersible granules, it still is that solid form exists and uses which kind of granulation aid, weighting agent etc. with liquid that active component content depends in part on active compound.Under the situation of water-dispersible granules, its active component content is for example 1-95 weight %, preferred 10-80 weight %.
In addition, the specific active ingredient preparation common agents that randomly contains tackiness agent, wetting agent, dispersion agent, emulsifying agent, permeate agent, sanitas, frostproofer and solvent, weighting agent, carrier and tinting material, defoamer, evaporation suppressor and change pH or viscosity respectively.
Formula (I) compound or its salt can itself form or use with the form of the preparation of itself and other pesticidal active substance (for example insecticide, miticide, nematocides, weedicide, sterilant, safener, fertilizer and/or growth regulator).
Can in the mixed preparation of The compounds of this invention or the mixed thing of bucket, use in conjunction with component for for example based on known activity composition to the inhibition of for example following material: acetolactate synthase for example, acetyl-CoA carboxylase, the Mierocrystalline cellulose synthetic enzyme, enol pyruvoyl shikimic acid-3-phosphate synthase, glutamine synthetase, p-hydroxybenzene pyruvic acid dioxygenase, phytoene desaturase, photosystem I, photosystem II, proporphyrinogen oxidase, as Weed Research 26 (1986) 441-445 or " The Pesticide Manual ", the 13rd edition, The British Crop Protection Council and the Royal Soc.of Chemistry, 2003 reach described in the document of wherein quoting.(described compound is to meet (the International Organization for Standardization of International Standards Organization for for example following activeconstituents for known weedicide that can combine with The compounds of this invention or plant-growth regulator, ISO) " popular name " or point out with chemical name or with code), and always comprise its all types of service, for example acid, salt, ester and isomer (for example steric isomer and optically active isomer).Herein with the mode of example pointed out its a kind of type of service and---some types of service in some cases---:
Acetochlor (acetochlor), activated esters (acibenzolar), benzo-thiadiazole (Acibenzolar-S-methyl), acifluorfen (acifluorfen, acifluorfen-sodium), aclonifen (aclonifen), alachlor (alachlor), two propylene grass Amine (allidochlor), grasses off (alloxydim, alloxydim-sodium), Ametryn (Ametryn), azole grass amine ketone (amicarbazone), first alachlor (amidochlor), acid ethyl Metsulfuron (amidosulfuron), ammonia grass pyridine (aminopyralid), sand grass strong (amitrole), ammonia Sulfonic acid ammonium (ammonium sulfamate), tricyclic benzene, ethyl alcohol (ancymidol), anilofos (Anilofos), Asulam (asulam), atrazine (atrazine), azole piperidine grass ketone (azafenidin), Yl-ethyl (azimsulfuron), azide-chun (aziprotryn), BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, fluorobutoxy Acyl alachlor (beflubutamid), Benazolin (benazolin, benazolin-ethyl), bencarbazone, B D F Ling (benfluralin), furosemide grass yellow (benfuresate), Bensulide (bensulide), Bensulfuron (bensulfuron-methyl), bentazone (Bentazone), double-benzene-ethyl metribuzin (benzfendizone), bicyclic Sulcotrione (Benzobicyclon), topiramate metribuzin (benzofenap), fomesafen (benzofluor), New Yan Ling (benzoylprop), carboxymethyl nitrofen (bifenox), double-alanyl phosphine (bialafos, bilanafos-sodium), Bispyribac (bispyribac, bispyribac-sodium), in addition to Grass and (bromacil), bromine butyrylcholinesterase metolachlor (bromobutide), bromophenol oxime (Bromofenoxim), bromoxynil (bromoxynil), chlorine bromine Long (bromuron), Turk grass (buminafos), hydroxyl grass ketone (busoxinone), butachlor (butachlor), Fluoropropionyl grass ethyl ester (butafenacil), weed suppression phosphorus (butamifos), butene metolachlor (Butenachlor), butralin (butralin), butoxy cyclic ketone (butroxydim), Gerbera enemy (butylate), azole metolachlor (cafenstrole), double-acyl metolachlor (carbetamide), Fluorine azole oxadiazon (carfentrazone, carfentrazone-ethyl), methoxy nitrofen (Chlomethoxyfen), grass off fear (chloramben), alkyne Wo Ling (chlorazifop, chlorazifop-butyl), chlorine bromine Long (chlorbromuron), chloroalkyne Ling (chlorbufam), Cutting grass g (chlorfenac, chlorfenac-sodium), oats ester (chlorfenprop), Methyl chloride fluorene hormone (chlorflurenol, chlorflurenol-methyl), chlorine grass Min (Chloridazon), herbicide (chlorimuron, chlorimuron-ethyl), dwarf Zhuang Su (chlormeq uat chloride), chlornitrofen (chlornitrofen), chlorophthalim, Methyl chloride phthalocyanine (chlorthal-dimethyl), Chlorotoluron (chlorotoluron), chlorsulfuron Long (chlorsulfuron), indolone grass ester (cinidon, cinidon-ethyl), cycloheptane Grass ether (cinmethylin), ethyl ether (cinosulfuron), clethodim (clethodim), Alkyne oxalic acid (clodinafop), alkyne grass ester (clodinafop-propargyl), hydrochloride acid gametocide (Clofencet), clomazone (clomazone), chloroformylphenoxy metolachlor (clomeprop), Tune acid (cloprop), clopyralid (clopyralid), chloro sulfonic acid ester (cloransulam, cloransulam-methyl), benzyl Long grass (cumyluron), cyanamide (cyanamide), Cyanazin (cyanazine), cyclopropyl amide acid (cyclanilide), ring grass enemy (cycloate), Cyclosulfamuron (cyclosulfamuron), bentazone ketone (cycloxydim), ring atrazine Long (Cycluron), Cyhalofop (cyhalofop, cyhalofop-butyl), sedge fast (Cyperquat), cyproterone Tianjin (cyprazine), propiconazole plug amine (cyprazole) ,2,4-D, 2,4-DB, Daimuron (daimuron / dymron), dry grass (dalapon), daminozide (Daminozide), dazomet (dazomet), decanol, beets Ann (desmedipham), Diquat net (desmetryn), detosyl-pyrazolate (DTP), oats enemy (diallate), Dicamba (dicamba), diuron nitrile (dichlobenil), 2,4 - drop acid (dichlorprop), Jing 2,4 - dichlorprop (dichlorprop-P), diclofop (diclofop, diclofop-methyl), diclofop-P-methyl, diclofenac sulfonamide alachlor (diclosulam), acetyl alachlor (diethatyl, diethatyl-ethyl), dry atrazine Long (difenoxuron), Ye Yan dry (difenzoquat), Fluazifop acid alachlor (diflufenican), two fluoropyrazole Long (diflufenzopyr, diflufenzopyr-sodium), oxazole Long (dimefuron), adjusting furosemide acid (Dikegulac-sodium), oxazole Long (dimefuron), piperazine Caodan (dimepiperate), Dimethyl-metolachlor (dimethachlor), isoamyl acetate net (dimethametryn), dimethyl thiophene Alachlor (dimethenamid), refined dimethyl thiophene metolachlor (dimethenamid-P), thiophene section due (Dimethipin), dimetrasulfuron, ammonium fluoride Ling (dinitramine), dinoseb (Dinoseb), special dinoseb (dinoterb), double-benzoyl-metolachlor (diphenamid), iso- C Net (dipropetryn), diquat (diquat, diquat-dibromide), sulfur fluoride Grass and (dithiopyr), diuron (diuron), DNOC, grass ended Tianjin (eglinazine-ethyl), Yin acid (endothal), EPTC, amyl Caodan (esprocarb), B butene F Ling (Ethalfluralin), Ethametsulfuron (ethametsulfuron-methyl), ethephon (Ethephon), methyl thiophene Long (ethidimuron), B metribuzin (ethiozin), B Oxygen furosemide grass yellow (ethofumesate), fluorine milk ether (ethoxyfen), fluorine milk ethyl ether (Ethoxyfen-ethyl), Ethoxysulfuron (ethoxysulfuron), Ethyl benzene metolachlor (Etobenzanid), F-5331 is N-[2 - chloro-4 - fluoro-5 - [4 - (3 - fluoro-propyl) -4,5 - dihydro-5 - Oxygen-1H-tetrazol-1 - yl] phenyl] ethanesulfonamide, 2,4,5 - tears acid (fenoprop), oxazole grasses Ling (fenoxaprop), fenoxaprop (fenoxaprop-P), fenoxaprop (Fenoxaprop-ethyl), fenoxaprop (fenoxaprop-P-ethyl), tetrazole Acyl alachlor (fentrazamide), non-grass Long (fenuron), fluorine Yan Ling (flamprop), Strong fluorine Yan Ling (flamprop-M-isopropyl), mefloquine Yan Ling (flamprop-M-methyl), Pyridine-ethyl (flazasulfuron), double-fluoro methyl alachlor (florasulam), fluazifop (Fluazifop), fine fluazifop (fluazifop-P), fluazifop-butyl (Fluazifop-butyl), fine fluazifop-butyl (fluazifop-P-butyl), iso- Topiramate grass ester (fluazolate), fluoroketone Sulfosulfuron (flucarbazone, flucarbazone-sodium), Fluoropyrazole Tribenuron (flucetosulfuron), chlorine B F Ling (fluchloralin), flufenacet (Flufenacet (thiafluamide)), fluorine-pyridazine grass ester (flufenpyr, flufenpyr-ethyl), amine fluoride Festival (flumetralin), azole ethyl alachlor (flumetsulam), Ene fluoride oxalate (flumiclorac, flumiclorac-pentyl), flumioxazin amine (Flumioxazin), alkyne metolachlor (flumipropyn), fluorine Long grass (fluometuron), Trifluoromethyl nitrate grass ether (fluorodifen), Fluoroglycofen ether (fluoroglycofen, fluoroglycofen-ethyl), amine fluoride grass azole (flupoxam), flupropacil, tetrafluoropropoxy Acid (flupropanate), fluoride pyridine-ethyl (flupyrsulfuron, flupyrsulfuron-methyl-sodium), 9 - hydroxy Wat formic acid (flurenol), fluorene-butyl (Flurenol-butyl), fluazinam metribuzin (fluridone), F 1,10 metribuzin (flurochloridone), Fluroxypyr (fluroxypyr, fluroxypyr-meptyl), furosemide ethyl alcohol (Flurprimidol), furosemide grass ketone (flurtamone), piperazine oxalic acid (fluthiacet), triazine Grass methyl (fluthiacet-methyl), thiazole oxamide (fluthiamide), fluorine sulfonamides Grass ether (fomesafen), formamide metsulfuron (foramsulfuron), Forchlorfenuron (Forchlorfenuron), kill wood phosphine (fosamine), furosemide oxygen grass ether (furyloxyfen), Gibberellin (gibberillic acid), glufosinate (glufosinate), L-glufosinate (L-glufosinate, L-glufosinate-ammonium), glufosinate (Glufosinate-ammonium), glyphosate (glyphosate), glyphosate isopropylamine salt (Glyphosate-isopropylammonium), H-9201, flunitrazepam sulfonamide (halosafen), Chloropyrazole ethyl (halosulfuron, halosulfuron-methyl), fluoropyrazole Wo Ling (Haloxyfop), fine fluoropyrazole Wo Ling (haloxyfop-P), fluoropyrazole Wo Ling ethoxyethyl (Haloxyfop-ethoxyethyl), Haloxyfop ethoxyethyl (Haloxyfop-P-ethoxyethyl), fluoro pyridine Wo Ling ester (haloxyfop-methyl), Haloxyfop methyl ester (haloxyfop-P-methyl), hexazinone (hexazinone), HNPC-9908, HOK-201, HW-02, Mi oxalic acid (imazamethabenz, imazamethabenz-methyl), methoxy imazethapyr (imazamox), A imazapyr (Imazapic), imazapyr (imazapyr), imidazole quinolinic acid (imazaquin), Imazethapyr (imazethapyr), zolpidem ethyl (imazosulfuron), lodging Amine (inabenfide), indanofan (indanofan), indole acetic acid (IAA), 4 - indole -3 - Butyric acid (IBA), iodine metsulfuron (iodosulfuron, iodosulfuron-methyl-sodium), iodobenzonitrile (ioxynil), Ding amidine amide (Isocarbamid), isopropyl pendimethalin (isopropalin), isoproturon (isoproturon), Isoxazole Long (isouron), isoxazole acid metolachlor (isoxaben), isobutyl ketone evil chlorine grass (Isoxachlortole), isoxazole grass ketone (isoxaflutole), Clomazone ether (Isoxapyrifop), IDH-100, KUH-043, KUH-071, special amine Ling (Karbutilate), ketospiradox, Lactofen (lactofen), Lenacil (Lenacil), linuron (linuron), maleic hydrazide (maleic hydrazide), MCPA, MCPB, MCPB methyl, MCPB ethyl, MCPB sodium 2 - methyl -4 - chloro-propionic acid (Mecoprop), 2 - methyl -4 - chloropropyl sodium, mecoprop-butotyl, mecoprop-P-butotyl, refined -2 ​​- methyl -4 - chloro acid dimethyl ammonium (Mecoprop-P-dimethylammonium), fine -2 - methyl -4 - chloro-propionic acid -2 - ethylhexyl (Mecoprop-P-2-ethylhexyl), fine -2 - methyl -4 - chloro potassium (Mecoprop-P-potassium), benzoth acyl metolachlor (mefenacet), chlorosulphonyl metolachlor (Mefluidide), A piperidine (mepiquat-chloride), A Sulfosulfuron (Mesosulfuron, mesosulfuron-methyl), mesotrione (mesotrione), Methyl benzoth Long (methabenzthiazuron), metam sodium (metam), oxazole acid grass Amine (metamifop), Metamitron (metamitron), pyrazole metolachlor (metazachlor), Herbicides azole (methazole), benzene grass ketone (methoxyphenone), methyl Daimuron (Methyldymron), 1 - MCP, methyl isothiocyanate, pyran Long (Metobenzuron), bromine Gu Long (metobromuron), metolachlor (Metolachlor), fine metolachlor (S-metolachlor), sulfonamide acetazolamide grass (Metosulam), methoxy Long (metoxuron), metribuzin (metribuzin), A Sulfosulfuron (metsulfuron, metsulfuron-methyl), Molinate (molinate), Heptanoylthio alachlor (monalide), monocarbamide, formamide sulfate (Monocarbamide dihydrogensulfate), Green Valley Long (monolinuron), single Ethyl (monosulfuron), monuron (monuron), MT 128, MT-5950 I.e. N-[3 - chloro-4 - (1 - methylethyl) phenyl] -2 - methyl-pentyl amide, NGGC-011, Naproanilide (Naproanilide), Napropamide (napropamide), naphthalene metolachlor (naptalam), NC-310, that is, 4 - (2,4 - dichloro-benzoyl) -1 - methyl-5 - benzyloxy pyrazole, long grass (Neburon), nicosulfuron (nicosulfuron), CFC-metolachlor (nipyraclofen), A sulfur pendimethalin (nitralin), nitrofen (nitrofen), Nitrophenola (mixed isomers Matter), nitrate fluoride grass ether (nitrofluorfen), azelaic acid, fluorine grass Min (norflurazon), Ping Caodan (orbencarb), ethyl aniline Tribenuron (orthosulfamuron), ammonia sulfur pendimethalin (Oryzalin), propyne Oxadiazon (oxadiargyl), oxadiazon (oxadiazon), Ethylene-ethyl (oxasulfuron), evil metribuzin (oxaziclomefone), oxyfluorfen Grass ether (oxyfluorfen), MET (paclobutrazole), paraquat (paraquat, paraquat dichloride), azelaic acid, pendimethalin (pendimethalin), pendralin, Five fluoro methyl alachlor (penoxsulam), A chlorine acid alachlor (pentanochlor), cyclopentyl Oxadiazon Ketone (pentoxazone), hwangcho volts (perfluidone), en-metolachlor (pethoxamid), Cotton amine Ning (phenisopham), Phenmedipham (phenmedipham, phenmedipham-ethyl), amlodipine pyridine acid (picloram), topiramate acyl fluoride alachlor (Picolinafen), pinoxaden (pinoxaden), piperazine grass phosphorus (piperophos), pirifenop, pirifenop-butyl, metolachlor (pretilachlor), Primisulfuron (Primisulfuron, primisulfuron-methyl), allyl phenyl thiazole (probenazole), Fluorine azole alachlor (profluazol), cyproterone cyanide Tianjin (procyazine), ammonia trifluralin (Prodiamine), cyproterone F Ling (profluraline), grass benzene ring ketone (profoxydim), Prohexadione (prohexadione), prohexadione calcium (prohexadione-calcium), Jasmine Ketone (prohydrojasmone), Prometon (prometon), prometryn (prometryn), Propachlor (propachlor), propanil (propanil), evil oxalic acid (propaquizafop), Propazine (propazine), aniline Ling (propham), Propisochlor (propisochlor), C Tribenuron (propoxycarbazone, propoxycarbazone-sodium), alkyne benzoyl Alachlor (propyzamide), sulfur imide grass (prosulfalin), prosulfocarb (prosulfocarb), Prosulfuron (prosulfuron), propargyl metolachlor (prynachlor), double-yl grass nitrile (pyraclonil), Topiramate grass ether (pyraflufen, pyraflufen-ethyl), pyrasulfotole, Pyrazolate (Pyrazolynate (pyrazolate)), topiramate ethyl (pyrazosulfuron-ethyl)), Benzyl grass azole (pyrazoxyfen), propyl ether grass (pyribambenz), isopropyl ether grass (Pyribambenz-isopropyl), pyrimidine grass oxime ether (pyribenzoxim), barnyardgrass Dan (Pyributicarb), pyridafol, Pyridate (pyridate), cyclic ester grass ether (pyriftalid), Grass ethyl ether (pyriminobac, pyriminobac-methyl), pyrimisulfan, ethyl grass Sulfide (pyrithiobac, pyrithiobac-sodium), pyroxasulfone, methoxy methyl grass Amine (pyroxsulam), Quinclorac (quinchlorac), quinolinic acid chloride A (Quinmerac), algae quinone (quinoclamine), quizalofop (quizalofop), Quizalofop ethyl ester (quizalofop-ethyl), Quizalofop (quizalofop-P), Quizalofop Ling ethyl (quizalofop-P-ethyl), quinoline Wo furfuryl acetate (quizalofop-P-tefuryl), Ethyl sulfone (rimsulfuron), sec-butyl-pass (secbumeton), sethoxydim pyridine (sethoxydim), Long grass ring (siduron), simazine (simazine), simetryne (simetryn), SN-106279, Sulcotrione (sulcotrione), vegetable grass fear (sulfallate (CDEC)), methanesulfonic alachlor (Sulfentrazone), methyl ethyl (sulfometuron, sulfometuron-methyl), Grass phosphinothioyl (sulfosate (glyphosate-trimesium)), Sulfosulfuron (sulfosulfuron), SYN-523, SYP-249, SYP-298, SYP-300, pasture amine (tebutam), Ding Thiophene Long (tebuthiuron), four oxygen-nitrobenzene (tecnazene), tefuryltrione, tembotrione, pyran grass ketone (tepraloxydim), terbacil (terbacil), Bent grass Ling (terbucarb), special Butachlor (terbuchlor), tert-pass (terbumeton), Terbuthylazine (terbuthylazine), terbutryn (terbutryne), TH-547, thiophene grass Amine (thenylchlor), thiafluamide, thiophene Freon (thiazafluron), thiazole smoke Acid (thiazopyr), thiadiazole metolachlor (thidiazimin), TDZ (thidiazuron), thiencarbazone, thiencarbazone-methyl, thifensulfuron (thifensulfuron, thifensulfuron-methyl), grasses Dan (thiobencarb), Chung Caodan (tiocarbazil), topramezone, tralkoxydim (tralkoxydim), Ye Yan Wei (triallate), ether Tribenuron (triasulfuron), triazine amine fluoride grass (triaziflam), triazofenamide, Tribenuron (tribenuron, tribenuron-methyl), trichloroacetic acid (TCA), three Chloropyrazole oxygen acid (triclopyr), herbicides ring (tridiphane), trietazine (trietazine), Trifloxysulfuron (trifloxysulfuron, trifloxysulfuron-sodium), trifluralin (Trfluralin), amine fluoride Tribenuron (triflusulfuron), metsulfuron methyl amine fluoride (Triflusulfuron-methyl), three Long (trimeturon), Trinexapac (trinexapac, trinexapac-ethyl), trifluoroacetic metsulfuron (tritosulfuron), tsitodef, Uniconazole (Uniconazole), fine Uniconazole (uniconazole-P), herbicides enemy (vernolate), ZJ-0166, ZJ-0270, ZJ-0543, ZJ-0862, and the following compounds ...
Figure BPA00001392541200441
Figure BPA00001392541200451
Special concern be to the control of the selectivity of noxious plant in useful plants and the ornamental plant crop.Though formula of the present invention (I) compound all has fabulous to enough selectivity in many crops, but in some crop, may produce phytotoxicity in principle, and mainly be to mix under the situation about using with the lower weedicide of other selectivity to crop plants.With regard to this point, the binding substances of formula of the present invention (I) compound of special concern is the binding substances that contains formula (I) compound or itself and other weedicide or sterilant and safener.Reduce---in for example important economically crop---plant toxicity side effect of used weedicide/sterilant with described safener to the effectively amount use of detoxifying, described crop is cereal (wheat, barley, rye, corn, rice, broomcorn millet), beet, sugarcane, rape, cotton and soybean for example, preferred cereal.
Described safener is preferably selected from:
S1) compound of formula (S1)
Figure BPA00001392541200452
Symbol wherein and affix have following implication:
n ANatural number for 0-5, preferred 0-3;
R A 1Be halogen, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group, nitro or (C 1-C 4) haloalkyl;
W AFor not being substituted or the substituted divalent heterocyclic group that is selected from the undersaturated or aromatic five-membered ring of the part that contains 1-3 heterocyclic atom, described heterocyclic atom is selected from N and O, has at least one N atom and O atom at the most in the wherein said ring; Be preferably and be selected from (W A 1) to (W A 4) group,
Figure BPA00001392541200461
m ABe 0 or 1;
R A 2Be OR A 3, SR A 3Or NR A 3R A 4Perhaps contain at least one N atom and 3 heteroatomic saturated or undersaturated 3-7 unit heterocycles that are preferably selected from O and S at the most, this heterocycle is connected on the carbonyl in (S1) by described N atom, and this heterocycle is unsubstituted or is selected from (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group or the optional phenyl groups replacement that replaces; Be preferably formula OR A 3, NHR A 4Or N (CH 3) 2Group, particularly formula OR A 3Group;
R A 3For hydrogen or be not substituted or the substituted aliphatic hydrocarbon group that preferably contains 1-18 carbon atom altogether;
R A 4Be hydrogen, (C 1-C 6) alkyl, (C 1-C 6) alkoxyl group or be substituted or unsubstituted phenyl;
R A 5Be H, (C 1-C 8) alkyl, (C 1-C 8) haloalkyl, (C 1-C 4) alkoxyl group-(C 1-C 8) alkyl, cyano group or COOR A 9, R wherein A 9Be hydrogen, (C 1-C 8) alkyl, (C 1-C 8) haloalkyl, (C 1-C 4) alkoxyl group-(C 1-C 8) alkyl, (C 1-C 6) hydroxyalkyl, (C 3-C 12) cycloalkyl or three-(C 1-C 4) the alkyl silyl;
R A 6, R A 7, R A 8Identical or different, be H, (C 1-C 8) alkyl, (C 1-C 8) haloalkyl, (C 3-C 12) cycloalkyl or be substituted or unsubstituted phenyl;
Preferably:
A) dichlorophenyl pyrazoline-3-carboxylic acid compound (S1 a), preferably such as 1-(2, the 4-dichlorophenyl)-5-(ethoxy carbonyl)-5-antazoline-3-carboxylic acid, 1-(2, the 4-dichlorophenyl)-compound of 5-(ethoxy carbonyl)-5-antazoline-3-carboxylic acid, ethyl ester (S1-1) (" mefenpyrdiethyl (mefenpyr-diethyl) "), and related compound, described in WO-A-91/07874;
B) derivative (S1 of dichlorophenyl pyrazole carboxylic acid b), preferably such as 1-(2, the 4-dichlorophenyl)-5-methylpyrazole-3-carboxyl acid ethyl ester (S1-2), 1-(2, the 4-dichlorophenyl)-5-sec.-propyl pyrazoles-3-carboxylic acid, ethyl ester (S1-3), 1-(2, the 4-dichlorophenyl)-5-(1, the 1-dimethyl ethyl) compound of pyrazoles-3-carboxylic acid, ethyl ester (S1-4), and related compound is described in EP-A-333 131 and EP-A-269 806;
C) 1, the derivative (S1 of 5-diphenylpypazole-3-carboxylic acid c), preferably such as the compound of 1-(2,4 dichloro benzene base)-5-phenylpyrazole-3-carboxylic acid, ethyl ester (S1-5), 1-(2-chloro-phenyl-)-5-phenylpyrazole-3-carboxylate methyl ester (S1-6), and related compound, described in EP-A-268554;
D) triazolylcarboxylic acid's compounds (S1 d), preferably such as fenchlorazole (fenchlorazole (ethyl)), promptly 1-(2, the 4-dichlorophenyl)-the 5-trichloromethyl-(1H)-1,2, the compound of 4-triazole-3-carboxylic acid, ethyl ester (S1-7), and related compound, described in EP-A-174 562 and EP-A-346 620;
E) 5-benzyl-or 5-phenyl-2-isoxazoline-3-carboxylic-acid or 5,5-phenylbenzene-2-isoxazoline-3-carboxylic acid compound (S1 e), preferably such as the compound of 5-(2, the 4-dichloro benzyl)-2-isoxazoline-3-carboxylic acid, ethyl ester (S1-8) or 5-phenyl-2-isoxazoline-3-carboxylic acid, ethyl ester (S1-9), and related compound, described in WO-A-91/08202; Or 5,5-phenylbenzene-2-isoxazoline carboxylic acid (S1-10) or 5,5-phenylbenzene-2-isoxazoline-carboxylic acid, ethyl ester (S1-11) (" isoxadifen (isoxadifen-ethyl) ") or 5,5-phenylbenzene-2-isoxazoline-carboxylic acid n-propyl (S1-12) or 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-13) are described in patent application WO-A-95/07897.
S2) the quinoline class of formula (S2),
Symbol wherein and affix have following implication:
R B 1Be halogen, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group, nitro or (C 1-C 4) haloalkyl;
n BIt is the natural number of 0-5, preferred 0-3;
R B 2Be OR B 3, SR B 3Or NR B 3R B 4Perhaps contain at least one N atom and 3 heteroatomic saturated or undersaturated 3-7 unit heterocycles that are preferably selected from O and S at the most, this heterocycle is connected on the carbonyl in (S2) by described N atom, and this heterocycle is unsubstituted or is selected from (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group or the optional phenyl groups replacement that replaces; Be preferably formula OR B 3, NHR B 4Or N (CH 3) 2Group, particularly formula OR B 3Group;
R B 3For hydrogen or be not substituted or the substituted aliphatic hydrocarbon group that preferably contains 1-18 carbon atom altogether;
R B 4Be hydrogen, (C 1-C 6) alkyl, (C 1-C 6) alkoxyl group or substituted or unsubstituted phenyl;
T BFor unsubstituted or by one or two (C 1-C 4) alkyl group or quilt [(C 1-C 3) alkoxyl group] (the C of carbonyl substituted 1Or C 2) alkane two basic chains;
Preferably:
A) 8-quinoline oxy phenylacetic acid compound (S2 a), preferred
(5-chloro-8-quinoline oxy) acetate 1-methyl polyhexamethylene (" cloquitocet_mexyl (cloquintocet-mexyl) ") (S2-1),
(5-chloro-8-quinoline oxy) acetate 1,3-dimethyl butyrate-1-base ester (S2-2),
(5-chloro-8-quinoline oxy) acetate 4-allyloxy butyl ester (S2-3),
(5-chloro-8-quinoline oxy) acetate 1-allyloxy third-2-base ester (S2-4),
(5-chloro-8-quinoline oxy) ethyl acetate (S2-5),
(5-chloro-8-quinoline oxy) methyl acetate (S2-6),
(5-chloro-8-quinoline oxy) allyl acetate (S2-7),
(5-chloro-8-quinoline oxy) acetate 2-(the inferior aminooxy of 2-propylidene)-1-ethyl ester (S2-8),
(5-chloro-8-quinoline oxy) acetate 2-oxygen third-1-base ester (S2-9), and related compound,
Described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366, and (5-chloro-8-quinoline oxy) acetate (S2-10), their hydrate and salt, for example its lithium salts, sodium salt, sylvite, calcium salt, magnesium salts, aluminium salt, molysite, ammonium salt, quaternary ammonium salt, sulfonium salt Huo phosphonium salt are described in WO-A-2002/34048;
B) (5-chloro-8-quinoline oxy) propanedioic acid compounds (S2 b), preferably such as the compound of (5-chloro-8-quinoline oxy) propanedioic acid diethyl ester, (5-chloro-8-quinoline oxy) propanedioic acid diallyl ester, (5-chloro-8-quinoline oxy) propanedioic acid methylethyl ester, and related compound, described in EP-A-0 582 198.
S3) compound of formula (S3)
Figure BPA00001392541200481
Symbol wherein and affix have following implication:
R C 1Be (C 1-C 4) alkyl, (C 1-C 4) haloalkyl, (C 2-C 4) thiazolinyl, (C 2-C 4) haloalkenyl group, (C 3-C 7) cycloalkyl, preferred dichloromethyl;
R C 2, R C 3Identical or different, be hydrogen, (C 1-C 4) alkyl, (C 2-C 4) thiazolinyl, (C 2-C 4) alkynyl, (C 1-C 4) haloalkyl, (C 2-C 4) haloalkenyl group, (C 1-C 4) alkyl-carbamoyl-(C 1-C 4) alkyl, (C 2-C 4) alkenyl amino formyl radical-(C 1-C 4) alkyl, (C 1-C 4) alkoxyl group-(C 1-C 4) alkyl, dioxolanyl-(C 1-C 4) alkyl, thiazolyl, furyl, furyl alkyl, thienyl, piperidyl, be substituted or unsubstituted phenyl; Perhaps R C 2And R C 3Form a substituted or unsubstituted heterocycle together, You Xuan oxazolidine, thiazolidine, piperidines, morpholine, hexahydropyrimidine or benzoxazine ring;
Preferably:
The dichloro acetamide active component, it is safener (soil effect safener) before being commonly used for seedling, for example
" dichlormide (dichlormid) " (=N, N-diallyl-2,2-dichloro acetamide) (S3-1),
" R-29148 " (3-dichloro-acetyl-2,2,5-trimethylammonium-1,3-oxazolidine) (S3-2), available from Stauffer,
" R-28725 " (3-dichloro-acetyl-2,2-dimethyl-1,3-oxazolidine) (S3-3), available from Stauffer,
" benoxacor (benoxacor) " (4-dichloro-acetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),
" PPG-1292 " (N-allyl group-N-[(1,3-dioxolane-2-yl) methyl] dichloro acetamide) (S3-5), available from PPG Industries,
" DKA-24 " (N-allyl group-N-[(allyl amino carbonyl) methyl] dichloro acetamide) (S3-6), available from Sagro-Chem,
" AD-67 " or " MON 4660 " (3-dichloro-acetyl-1-oxa--3-azepine-spiral shell [4,5] decane) (S3-7), available from Nitrokemia or Monsanto,
" TI-35 " (1-dichloro-acetyl azepan) (S3-8), available from TRI-Chemical RT,
" diclonon " (dicyclonone) or " BAS145138 " or " LAB145138 " ((RS)-1-dichloro-acetyl-3,3,8a-trimethylammonium perhydro pyrrolo-[1,2-a] pyrimidine-6-ketone) (S3-9), available from BASF,
" furilazole (furilazole) " or " MON 13900 " ((RS)-3-dichloro-acetyl-5-(2-furyl)-2,2-Er Jia Ji oxazolidine) are (S3-10); And (R)-isomer (S3-11).
S4) the N-acyl group sulfonamides and the salt thereof of formula (S4),
Figure BPA00001392541200501
Symbol wherein and affix have following implication:
X DBe CH or N;
R D 1Be CO-NR D 5R D 6Or NHCO-R D 7
R D 2Be halogen, (C 1-C 4) haloalkyl, (C 1-C 4) halogenated alkoxy, nitro, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group, (C 1-C 4) alkyl sulphonyl, (C 1-C 4) alkoxy carbonyl or (C 1-C 4) alkyl-carbonyl;
R D 3Be hydrogen, (C 1-C 4) alkyl, (C 2-C 4) thiazolinyl or (C 2-C 4) alkynyl;
R D 4Be halogen, nitro, (C 1-C 4) alkyl, (C 1-C 4) haloalkyl, (C 1-C 4) halogenated alkoxy, (C 3-C 6) cycloalkyl, phenyl, (C 1-C 4) alkoxyl group, cyano group, (C 1-C 4) alkylthio, (C 1-C 4) alkyl sulphinyl, (C 1-C 4) alkyl sulphonyl, (C 1-C 4) alkoxy carbonyl or (C 1-C 4) alkyl-carbonyl;
R D 5Be hydrogen, (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 5-C 6) cycloalkenyl group, phenyl or contain v DThe individual first heterocycle of heteroatomic 3-6 that is selected from nitrogen, oxygen and sulphur, 7 groups wherein mentioning at last are by v DIndividually be selected from following substituting group and replace: halogen, (C 1-C 6) alkoxyl group, (C 1-C 6) halogenated alkoxy, (C 1-C 2) alkyl sulphinyl, (C 1-C 2) alkyl sulphonyl, (C 3-C 6) cycloalkyl, (C 1-C 4) alkoxy carbonyl, (C 1-C 4) alkyl-carbonyl and phenyl, and for cyclic group, also can be by (C 1-C 4) alkyl and (C 1-C 4) the haloalkyl replacement;
R D 6Be hydrogen, (C 1-C 6) alkyl, (C 2-C 6) thiazolinyl or (C 2-C 6) alkynyl, 3 groups wherein mentioning at last are selected from halogen, hydroxyl, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group and (C 1-C 4) v of alkylthio DIndividual group replaces, or
R D 5And R D 6Form a pyrrolidyl or piperidyl group with its nitrogen-atoms that carries;
R D 7Be hydrogen, (C 1-C 4) alkylamino, two (C 1-C 4) alkylamino, (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl, 2 groups wherein mentioning at last are by v DIndividual the halogen, (C of being selected from 1-C 4) alkoxyl group, (C 1-C 6) halogenated alkoxy and (C 1-C 4) substituting group of alkylthio replaces, and for cyclic group, also can be by (C 1-C 4) alkyl and (C 1-C 4) the haloalkyl replacement;
n DBe 0,1 or 2;
m DBe 1 or 2;
v DBe 0,1,2 or 3;
Wherein preferred compound is a N-acyl group sulfamide compound, for example is known in for example following formula (S4 of WO-A-97/45016 a) N-acyl group sulfamide compound
Figure BPA00001392541200511
Wherein
R D 7Be (C 1-C 6) alkyl, (C 3-C 6) cycloalkyl, 2 groups wherein mentioning at last are by v DIndividually be selected from following substituting group and replace: halogen, (C 1-C 4) alkoxyl group, (C 1-C 6) halogenated alkoxy and (C 1-C 4) alkylthio, and for cyclic group, also can be by (C 1-C 4) alkyl and (C 1-C 4) the haloalkyl replacement;
R D 4Be halogen, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group, CF 3
m DBe 1 or 2;
v DBe 0,1,2 or 3;
And
Acyl group sulfamyl benzamides for example is known in for example following formula (S4 of WO-A-99/16744 b) acyl group sulfamyl benzamides,
Figure BPA00001392541200512
These compounds for example: wherein
R D 5=cyclopropyl, and (R D 4)=2-OMe (" cyclopropyl-sulfonylamide (cyprosulfamide) ", S4-1),
R D 5=cyclopropyl, and (R D 4)=5-Cl-2-OMe (S4-2),
R D 5=ethyl, and (R D 4)=2-OMe (S4-3),
R D 5=sec.-propyl, and (R D 4)=5-Cl-2-OMe (S4-4) and
R D 5=sec.-propyl, and (R D 4)=2-OMe (S4-5),
And
Be known in for example formula (S4 of EP-A-365484 c) N-acyl group sulfamyl phenyl ureas compound
Figure BPA00001392541200521
Wherein
R D 8And R D 9Be hydrogen, (C independently of one another 1-C 8) alkyl, (C 3-C 8) cycloalkyl, (C 3-C 6) thiazolinyl, (C 3-C 6) alkynyl,
R D 4Be halogen, (C 1-C 4) alkyl, (C 1-C 4) alkoxyl group, CF 3,
m DBe 1 or 2;
For example
1-[4-(N-2-anisoyl sulfamyl) phenyl]-3-methyl urea,
1-[4-(N-2-anisoyl sulfamyl) phenyl]-3, the 3-dimethyl urea,
1-[4-(N-4,5-dimethylbenzoyl sulfamyl) phenyl]-3-methyl urea.
S5) activeconstituents (S5) of the hydroxyl aromatic same clan and aromatic-aliphatic carboxylic acid derivative class, for example 3,4,5-triacetyl aminobenzoic acid ethyl ester, 3,5-dimethoxy-4 '-hydroxy-benzoic acid, 3,5-resorcylic acid, 4-hydroxyl Whitfield's ointment, 4-fluorosalicylic acid, 2 hydroxy cinnamic acid 98,2, the 4-dichloro-cinnamic acid is described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
S6) 1,2-dihydro-quinoxaline-2-ketone activeconstituents (S6), for example
1-methyl-3-(2-thienyl)-1; 2-dihydro-quinoxaline-2-ketone, 1-methyl-3-(2-thienyl)-1; 2-dihydro-quinoxaline-2-thioketones, 1-(2-aminoethyl)-3-(2-thienyl)-1; 2-dihydro-quinoxaline-2-keto hydrochloride, 1-(2-methyl sulphonyl amino-ethyl)-3-(2-thienyl)-1; 2-dihydro-quinoxaline-2-ketone is described in WO-A-2005/112630.
S7) compound of formula (S7) is described in WO-A-1998/38856
Figure BPA00001392541200531
Symbol wherein and affix have following implication:
R E 1, R E 2Be halogen, (C independently of one another 1-C 4) alkyl, (C 1-C 4) alkoxyl group, (C 1-C 4) haloalkyl, (C 1-C 4) alkylamino, two (C 1-C 4) alkylamino, nitro,
A EBe COOR E 3Or COSR E 4,
R E 3, R E 4Be hydrogen, (C independently of one another 1-C 4) alkyl, (C 2-C 6) thiazolinyl, (C 2-C 4) alkynyl, cyano group alkyl, (C 1-C 4) haloalkyl, phenyl, nitrophenyl, benzyl, halogeno-benzyl, pyridyl alkyl and alkylammonium,
n E 1Be 0 or 1,
n E 2, n E 3Be 0,1 or 2 independently of one another,
Preferably:
The diphenylmethyl ethoxyacetic acid,
Diphenylmethyl ethoxyacetic acid ethyl ester,
Phenylbenzene methoxy menthyl acetate (CAS registration number: 41858-19-9) (S7-1).
S8) compound of formula (S8), described in WO-A-98/27049, or its salt
Figure BPA00001392541200532
Wherein
X FBe CH or N,
n FIf X F=N, then n FRepresent an integer among the 0-4, if X F=CH, then n FRepresent an integer among the 0-5,
R F 1Be halogen, (C 1-C 4) alkyl, (C 1-C 4) haloalkyl, (C 1-C 4) alkoxyl group, (C 1-C 4) halogenated alkoxy, nitro, (C 1-C 4) alkylthio, (C 1-C 4) alkyl sulphonyl, (C 1-C 4) alkoxy carbonyl, the optional phenyl that replaces, the optional phenoxy group that replaces,
R F 2Be hydrogen or (C 1-C 4) alkyl,
R F 3Be hydrogen, (C 1-C 8) alkyl, (C 2-C 4) thiazolinyl, (C 2-C 4) alkynyl or aryl, wherein above-mentioned each carbon-containing group of mentioning is unsubstituted or by one or more---preferably at the most 3---, and the identical or different group that is selected from halogen and alkoxyl group replaces;
Be preferably as follows compound or its salt: wherein
X FBe CH,
n FBe an integer among the 0-2,
R F 1Be halogen, (C 1-C 4) alkyl, (C 1-C 4) haloalkyl, (C 1-C 4) alkoxyl group, (C 1-C 4) halogenated alkoxy,
R F 2Be hydrogen or (C 1-C 4) alkyl,
R F 3Be hydrogen, (C 1-C 8) alkyl, (C 2-C 4) thiazolinyl, (C 2-C 4) alkynyl or aryl, wherein above-mentioned each carbon-containing group of mentioning is unsubstituted or by one or more---preferably at the most 3---, and the identical or different group that is selected from halogen and alkoxyl group replaces.
S9) 3-(5-tetrazyl carbonyl)-2-quinolones activeconstituents (S9), for example 1,2-dihydro-4-hydroxyl-1-ethyl-3-(5-tetrazyl carbonyl)-2-quinolone (CAS registration number: 219479-18-2), 1,2-hydrogen-4-hydroxyl-1-methyl-3-(5-tetrazyl carbonyl)-2-quinolone (the CAS registration number: 95855-00-8), described in WO-A-1999/000020.
S10) formula (S10 a) or (S10 b) compound, described in WO-A-2007/023719 and WO-A-2007/023764
Figure BPA00001392541200541
Wherein
R G 1Be halogen, (C 1-C 4) alkyl, methoxyl group, nitro, cyano group, CF 3, OCF 3Y G, Z GBe O or S independently of one another,
n GBe an integer among the 0-4,
R G 2Be (C 1-C 16) alkyl, (C 2-C 6) thiazolinyl, (C 3-C 6) cycloalkyl, aryl; Benzyl, halogeno-benzyl,
R G 3Be hydrogen or (C 1-C 6) alkyl.
S11) activeconstituents (S11) of oxygen base imino-compound class, it is known seed dressing, for example
" oxabetrinil (oxabetrinil) " ((Z)-1,3-dioxolane-2-ylmethoxy imino-(phenyl) acetonitrile) (S11-1), known its is to be used for the seed dressing safener that broomcorn millet is resisted metolachlor infringement,
" fluxofenim (fluxofenim) " (1-(4-chloro-phenyl-)-2,2,2-three fluoro-1-ethyl ketone O-(1,3-dioxolane-2-ylmethyl) oxime (S11-2), known its be used for broomcorn millet resist metolachlor infringement the seed dressing safener and
" cyometrinil (cyometrinil) " or " CGA-43089 " ((Z)-cyano group methoxyimino (phenyl) acetonitrile) (S11-3), known its is to be used for the seed dressing safener that broomcorn millet is resisted metolachlor infringement.
S12) different sulfo-benzodihydropyrone class (isothiochromanone) activeconstituents (S12), for example [(3-oxygen-1H-2-benzo thiapyran-4 (3H)-subunit) methoxyl group] methyl acetate (CAS registration number: the 205121-04-6) related compound among (S12-1) and the WO-A-1998/13361.
S13) one or more are selected from following compound (S13):
" naphthalic anhydride " (1,8-naphthalene dicarboxylic acids acid anhydride) (S13-1), known its is to be used for the seed dressing safener that corn is resisted thiocarbamate herbicide infringement,
" fenclorim (fenclorim) " (4,6-two chloro-2-phenyl pyrimidines) (S13-2), known its is the safener that is used for resisting the rice third careless amine (pretilachlor) of sowing,
" separate careless amine (flurazole) " (2-chloro-4-Trifluoromethyl-1,3-thiazole-5-carboxylic acid benzyl ester) (S13-3), known its is to be used for the seed dressing safener that broomcorn millet is resisted the infringement of alachlor and metolachlor,
" CL-304415 " (the CAS registration number: 31541-57-8) (4-carboxyl-3,4-dihydro-2H-1-chromene-4-acetate) (S13-4), available from American Cyanamid, known its is to be used for the safener that corn is resisted imidazolone infringement,
" MG-191 " (the CAS registration number: 96420-72-3) (2-dichloromethyl-2-methyl isophthalic acid, 3-dioxolane) (S13-5), available from Nitrokemia, known its is the safener that is used for corn,
" MG-838 " (the CAS registration number: 133993-74-5) (1-oxa--4-azaspiro [4.5] decane-4-dithionic acid 2-propylene ester) (S13-6), available from Nitrokemia,
" thiodemeton (disulfoton) " (S-2-ethylmercapto group diethyldithioposphoric acid O, O-diethyl ester) (S13-7),
" synergy phosphorus (dietholate) " (O-phenyl thiophosphoric acid O, O-diethyl ester) (S13-8),
" mephenate " (4-Chlorophenylmethyl carbamate) (S13-9).
S14) except noxious plant being had herbicide effect, also crop plants (for example rice) is had the activeconstituents of safener effect, for example,
" dimepiperate (dimepiperate) " or " MY-93 " (piperidines-1-bamic acid S-1-methyl isophthalic acid-phenylethylester), known its are used for the safener that rice is resisted the infringement of molinate (molinate) weedicide,
" daimuron (daimuron) " or " SK 23 " (1-(1-methyl isophthalic acid-phenylethyl)-3-p-methylphenyl urea), known its are to be used for the safener that rice is resisted the infringement of imazosulfuron (imazosulfuron) weedicide,
" cumyluron (cumyluron) "=" JC-940 " (3-(2-Chlorophenylmethyl)-1-(1-methyl isophthalic acid-phenylethyl) urea, referring to JP-A-60087254, known its is to be used for the safener that rice is resisted the infringement of some weedicide,
" methoxyphenone (methoxyphenone) " or " NK 049 " (3,3 '-dimethyl-4-methoxy benzophenone), known its is to be used for the safener that rice is resisted the infringement of some weedicide,
" CSB " (1-bromo-4-(chloromethyl alkylsulfonyl) benzene), available from Kumiai, (the CAS registration number: 54091-06-4), known its is to be used for the safener that rice is resisted the infringement of some weedicide.
S15) mainly as weedicide, in addition crop plants had the activeconstituents of safener effect, for example
(2,4 dichloro benzene oxygen base) acetate (2,4-D),
(4-chlorophenoxy) acetate,
(R, S)-2-(4-chloro-oxy-o-cresyl) propionic acid (2-first-4-chloropropionic acid (mecoprop)),
4-(2,4 dichloro benzene oxygen base) butyric acid (2,4-DB),
(4-chloro-oxy-o-cresyl) acetate (MCPA),
4-(4-chloro-oxy-o-cresyl) butyric acid,
4-(4-chlorophenoxy) butyric acid,
3,6-two chloro-O-Anisic Acids (dicamba 98),
3,6-two chloro-O-Anisic Acid 1-(ethoxy carbonyl) ethyl esters (lactidichlor-ethyl).
In the described safener some are known as weedicide, therefore, except that noxious plant is had the herbicide effect, also crop plants formed provide protection simultaneously.
The weight ratio of weedicide (mixture) and safener depends on the effectiveness of the rate of application and the concrete safener of weedicide usually, and can in wide region, change, for example 200: 1 to 1: 200, preferred 100: 1 to 1: 100, particularly in 20: 1 to 1: 20 the scope.Described safener can be similar to the mixture of formula (I) compound or itself and other weedicide/sterilant and prepare, and can provide with the form of promptly mixing thing or the mixed thing of bucket of weedicide and use.
For using, if suitable, will dilute in a usual manner, for example dilute with water under the situation of spraying pulvis, missible oil, dispersion agent and water-dispersible granules with the preparation that the standard available form exists.Powderous preparations, soil and broadcast sowing granule and the sprayable solution preparation no longer diluted with other inert substance usually before using.
Especially, the required rate of application of formula (I) compound changes with external conditions (for example temperature, humidity, used weedicide type).It can change in wide region, for example 0.001 and 10.0kg or more active substance/ha between, but preferably 0.005 and 5kg/ha between.
The present invention will be described in more detail with reference to embodiment below, but it should not limit the present invention by any way.
A. synthetic embodiment
Preparation embodiment:
2-amino-4-indanyl-1-amino-6-methylpyrimidine (example: 1.4)
With the 145 ℃ of heating 3 hours in the 30ml dimethyl formamide of the mixture of 2.9g (20mmol) 2-amino-4-chloro-6-methylpyrimidine, 2.9g (22mmol) 1-aminoidan and 4.1g (30mmol) salt of wormwood.After the cooling, this reaction mixture of hydrolysis with this aqueous mixture of dichloromethane extraction, uses dried over sodium sulfate through isolated organic phase.Filtering out described siccative and, the ethyl acetate/methanol/triethylamine of crude mixture by column chromatography use 90/10/1 separated as elutriant by after the evaporation concentration organic phase.To be dissolved in 2: 8 the ethyl acetate/heptane with 2-amino-4-indanyl-1-amino-6-methylpyrimidine that this mode obtains and use activated carbon treatment.Isolate gac and by after the evaporation concentration solvent, obtaining 1g2-amino-4-indanyl-1-amino-6-methylpyrimidine (vitreous solid, m.p:53-54 ℃, productive rate is 20%, purity is 95%).
N4-[(1R, 2S)-2,6-dimethyl-2,3-dihydro-1H-indenes-1-yl]-6-(trifluoromethyl) pyrimidine-2,4-diamines (example: 1.27)
With 0.3g (1.5mmol) 2-amino-4-chloro-6-trifluoromethyl pyrimidine, 0.3g (1.5mmol) (1R, 2S)-2,6-dimethyl-2, the mixture of 3-dihydro-1H-indenes-1-ammonia chloride and 0.53g (3.8mmol) salt of wormwood heated 5 hours at 120 ℃ in the 3ml dimethyl formamide.After the cooling, reaction mixture adsorbed with silica gel and use ethyl acetate/heptane to carry out purifying as elutriant by column chromatography.By after the evaporation concentration, obtain 0.24g solid state N 4-[(1R, 2S)-2,6-dimethyl-2,3-dihydro-1H-indenes-1-yl]-6-(trifluoromethyl) pyrimidine-2,4-diamines (productive rate is 44%, and purity is 90%).
Divide many parts (every part of about 5g) to add in the mixture of 85ml phosphoryl chloride and 47.5ml xylidine 33.4g (0.186mol) 4-hydroxyl-6-trifluoromethyl pyrimidine-2-base amine, and this mixture heating up is refluxed, dissolve until the solid that adds.Then this mixture reheat was refluxed 90 minutes.After the cooling, under observing the situation of phosphoryl chloride safety rule, this reaction mixture is added in the frozen water.Use the dichloromethane extraction water, isolate organic phase and use dried over sodium sulfate, filter out this siccative.After evaporation concentration, obtain the 47.8g crude mixture.Carry out column chromatography with ethyl acetate/heptane as elutriant and separate, obtain 8.5g 4-chloro-6-trifluoromethyl pyrimidine-2-base amine (solid-state, productive rate is 22%, and purity is 95%) afterwards.
5-chloro-N4-[(1R, 2S)-2,6-dimethyl-2,3-dihydro-1H-indenes-1-yl]-6-(trifluoromethyl) pyrimidine-2,4-diamines (example: 1.38)
With 0.10g (0.43mmol) 4,5-two chloro-6-(trifluoromethyl) pyrimidine-2-amine, 0.08g (0.51mmol) (1R, 2S)-2,6-dimethyl-2, the mixture of 3-dihydro-1H-indenes-1-amine and 0.14g (1.3mmol) salt of wormwood in solvent 1ml N,N-DIMETHYLACETAMIDE in microwave device (Biotage Initiator, http://www.biotage.com/DynPage.aspx? id=22001) heated 30 minutes in 125 ℃ in.After crude mixture absorbed with silica gel, carry out column chromatography and separate, obtain the 5-chloro-N4-[(1R of 0.089g, 2S)-2,6-dimethyl-2,3-dihydro-1H-indenes-1-yl]-6-(trifluoromethyl) pyrimidine-2,4-diamines (solid-state, productive rate is 55%, and purity is 95%).
2-amino-4-phenyl-6-[(1R)-1,2,3,4-tetralin-1-base is amino] pyrimidine-5-formonitrile HCN (example: 1.53)
With 0.40g (1.21mmol) 2-amino-4-chloro-6-phenyl pyrimidine-5-formonitrile HCN (crude mixture, as precursor, purity about 70%), 0.27g (1.82mmol) (1R, 2S)-2,6-dimethyl-2, the mixture of 3-dihydro-1H-indenes-1-amine and 0.34g (2.42mmol) salt of wormwood in solvent 1ml N-Methyl pyrrolidone at microwave device (Biotage Initiator, http://www.biotage.com/DynPage.aspx? id=22001) heated 60 minutes in 150 ℃ in.Crude mixture is absorbed with silica gel, carries out column chromatography subsequently and separate, obtain that 2-amino-4-phenyl of 0.291g-6-[(1R)-1,2,3,4-tetralin-1-base is amino] pyrimidine-5-formonitrile HCN (solid-state, productive rate is 67%, and purity is 95%).
With 6.6g (31.1mmol) 2-amino-6-oxygen-4-phenyl-1,6-dihydro-pyrimidin-5-formonitrile HCN divides many parts (every part of about 1g) to add in the mixture of 50ml phosphoryl chloride and 0.5ml xylidine, and this mixture heating up is refluxed, and dissolves until the solid that adds.Then this mixture reheat was refluxed 90 minutes.After the cooling, under observing the situation of phosphoryl chloride safety rule, this reaction mixture is added in the frozen water.Use the dichloromethane extraction water, isolate organic phase and use dried over sodium sulfate, filter out this siccative.After evaporation concentration, (solid-state, purity is about 70%, and wherein mixing has 2-amino-6-oxygen-4-phenyl-1,6-dihydro-pyrimidin-5-formonitrile HCN and xylidine to obtain 2-amino-4-chloro-6-phenyl pyrimidine-5-formonitrile HCN of 3.2g; This crude mixture can need not to be further purified and be used in the later stages).
With 7.6ml (7.4g, density is 0.98g/l, 30% sodium methoxide solution that is commercially available 41.2mmol) dropwise adds in the mixture of 80ml methyl alcohol, 5.5g (34.5mmol) N-cyano group benzene carboxylic imide acid methyl esters and 2.9g (34.5mmol) malonamide nitrile.With this reaction mixture reflux 120 minutes, cool off this mixture and by evaporation concentration, and residual residuum is soluble in water.Use in the vitriol oil then and water, and isolate precipitated solid.After the drying, obtain 2-amino-6-oxygen-4-phenyl-1 of 6.78g, 6-dihydro-pyrimidin-5-formonitrile HCN (solid-state, purity about 95%).
N4-[(1R)-1,2,3,4-tetralin-1-yl]-5-(trifluoromethyl) pyrimidine-2,4-diamines (example: 1.60)
Under whipped state, with 2 of 1.0g, 4-two chloro-5-(trifluoromethyl) pyrimidines (the Aldrich subscription number is 684864) add to and are cooled in about 5 ℃ methanol ammonium hydroxide solution (about 8mol ammonia is in methyl alcohol), stir 2 hours with this mixture heating up to 25 ℃ and in this temperature.By this mixture of evaporation concentration and add in the water.After the suction filtration, obtain the 4-amino-2-chloro-5-trifluoromethyl pyrimidine (about 45%) of 0.56g and the mixture of 2-amino-4-chloro-5-trifluoromethyl pyrimidine (about 45%).
Then, obtain 0.25g in the solid and 0.224g (1.47mmol) (R)-1 with above, 2,3, the mixture of 4-tetrahydrochysene-1-ALPHA-NAPHTHYL AMINE and 0.35g (2.53mmol) salt of wormwood in 1mlN-crassitude ketone solvent in the inherent microwave device of confined chamber (closed cell) (Biotage Initiator, http://www.biotage.com/DynPage.aspx? id=22001) heated 60 minutes in 160 ℃ in.Crude mixture is absorbed with silica gel, and, obtains the N4-[(1R of 0.190g by the column chromatography after separating)-1,2,3,4-tetralin-1-yl]-5-(trifluoromethyl) pyrimidine-2,4-diamines (wax shape, purity are 95%).
The chemical physics data:
Figure BPA00001392541200601
Figure BPA00001392541200611
Figure BPA00001392541200621
Figure BPA00001392541200631
Figure BPA00001392541200641
Figure BPA00001392541200651
Figure BPA00001392541200661
Figure BPA00001392541200681
B. example of formulations
A) powder composition obtains by 10 weight part formula (I) compounds and/or its salt and 90 weight parts are mixed to be incorporated in to pulverize in the pulverizer as the talcum of inert substance.
B) easily be scattered in the water wettable powder by with 25 weight part formula (I) compounds and/or its salt, 64 weight parts as containing of inert substance kaolinic quartz, 10 weight part lignin sulfonic acid potassiums and 1 weight part mix to be incorporated in to pulverize in the pin formula shredder (pin mill) as the oleoyl N-methyltaurine sodium of wetting agent and dispersion agent and obtain.
C) easily be scattered in the water the dispersion enriching agent by with 20 weight part formula (I) compounds and/or its salt, 6 weight part alkyl phenol polyoxyethylene glycol ethers (
Figure BPA00001392541200682
Triton X 207), different tridecyl alcohol polyglycol ethers of 3 weight parts (8EO) and 71 weight part paraffin mineral oil (boiling range for for example about 255 to greater than 277 ℃) mix and are incorporated in that to be ground to fineness in the ball milling be to obtain below 5 microns.
D) missible oil is obtained as the pimelinketone of solvent and the 10 weight parts oxygen ethylization nonyl phenol as emulsifying agent by 15 weight part formula (I) compounds and/or its salt, 75 weight parts.
E) water-dispersible granules by following component is mixed, with this mixture pin formula grinding machine for grinding and in fluidized-bed by spraying as the water of granulation liquid and the described powder of granulation obtains:
75 weight part formula (I) compounds and/or its salt,
The calcium lignosulfonate of 10 weight parts,
5 weight part Sodium Lauryl Sulphate BP/USPs,
3 weight account polyethylene alcohol and
7 weight part kaolin.
F) water-dispersible granules also can by in homogenizing on the colloidal mill and the following component of precomminution, in sand mill, grind subsequently, and will in spray tower, use one-component nozzle to atomize with the suspension that this mode obtains and drying obtains:
25 weight part formula (I) compounds and/or its salt,
5 weight parts 2,2 '-dinaphthyl methane-6,6 '-sodium disulfonate,
2 weight part oleoyl N-methyltaurine sodium,
1 weight account polyethylene alcohol,
17 weight part lime carbonate and
50 weight parts waters.
C. biology embodiment
The description of test
1. herbicide effect and crop plants consistency before the seedling
The seed of unifacial leaf or broadleaf weed plant or crop plants is planted in the sandy loam in the wood fibre basin, and cover with soil.The The compounds of this invention that will be formulated as wettable powder (WP) or missible oil (EC) form then is applied to the surface of overburden soil under the water rate of application of 600-800l/ha (scaled value) with the form of waterborne suspension or emulsion under the situation of adding 0.2% wetting agent.
After processing, basin is placed the greenhouse, and make it to remain under the test plant better growing conditions.After 3 all test periods, by comparing with untreated control group, (weeding activity is in per-cent (%): 100% activity=plant is death all for the injured degree of visually rank test plant; 0% activity=identical) with adjoining tree.
Abbreviation below in following table, using:
ABUTH: hemp (Abutilon theophrasti)
ALOMY: big fringe amur foxtail (Alopecurus myosuroides)
AMARE: Amaranthus retroflexus (Amaranthus retroflexus)
CHEAL: lamb's-quarters (Chenopodium album)
CYPES: cyperus esculentus (Cyperus esculentus)
ECHCG: barnyard grass grass (Echinochloa crus-galli)
LOLMU: Itanlian rye (Lolium multiflorum)
MATIN: odorless german chamomile (Matricaria inodora)
POLCO: volume stem knotweed (Polygonum convolvulus)
PHBPU: purple lead a cow (Pharbitis purpurea)
SETVI: Herba Setariae Viridis (Setaria viridis)
STEME: chickweed (Stellaria media)
VERPE: Arabic veronica (Veronica persica)
VIOTR: wild pansy (Viola tricolor)
Table 1: herbicide effect before the seedling
Figure BPA00001392541200701
The result shows, The compounds of this invention has herbicide effect before the good seedling to the weeds of wide spectrum and weeds.For example, the compound in the table 1 with per hectare 0.32kg with when still less the rate of application of active substance is used with Miao Qianfa, has fabulous herbicide effect to noxious plant (for example chickweed, barnyard grass grass, Itanlian rye, Herba Setariae Viridis, Amaranthus retroflexus and big fringe amur foxtail).
2. postemergence weed control effect and crop plants consistency
The seed of unifacial leaf or broadleaf weed plant or crop plants is planted in the sandy loam in the wood fibre basin, and cover, and make it in the greenhouse, to grow under the better growing conditions with soil.After planting 2 to 3 weeks, handle test plant in a leaf phase.The compounds of this invention form with waterborne suspension or emulsion under the situation of adding 0.2% wetting agent that will be formulated as wettable powder (WP) or missible oil (EC) form then is sprayed to the green plants position under the water rate of application of 600-800l/ha (scaled value).Test plant is placed about 3 weeks under optimal growth condition in the greenhouse after, by with untreated control group relatively, (weeding activity is in per-cent (%): 100% activity=plant is death all for the activity of visually rank preparation; 0% activity=identical) with adjoining tree.
Table 2: postemergence weed control effect
Figure BPA00001392541200711
The result shows that The compounds of this invention has good postemergence weed control effect to the weeds and the weeds of wide spectrum.For example, the compound in the table 2 with per hectare 0.32kg with when still less the rate of application of active substance is used with Miao Houfa, has fabulous herbicide effect to noxious plant (for example barnyard grass grass, hemp and Amaranthus retroflexus).

Claims (20)

1. compatible salt on the compound of formula (I) and the agrochemistry thereof
Figure FPA00001392541100011
Wherein
R 1And R 2Be independently from each other
-hydrogen, halogen, hydroxyl, cyano group, nitro, amino, C (O) OH, C (O) NH 2
-(C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 1-C 6) alkyl-carbonyl, (C 1-C 6) halogenated alkyl carbonyl, (C 1-C 6) alkyl-carbonyl oxygen base, (C 1-C 6) halogenated alkyl carbonyl oxygen base, (C 1-C 6) alkyl-carbonyl-(C 1-C 4) alkyl;
-(C 1-C 6) alkoxyl group, (C 1-C 6) halogenated alkoxy, (C 1-C 6) alkoxy carbonyl, (C 1-C 6) halo alkoxy carbonyl, (C 1-C 6) alkoxy carbonyl-(C 1-C 6) alkyl, (C 1-C 6) halo alkoxy carbonyl-(C 1-C 6) alkyl, (C 1-C 6) alkoxy carbonyl-(C 1-C 6) haloalkyl, (C 1-C 6) halo alkoxy carbonyl-(C 1-C 6) haloalkyl;
-(C 2-C 6) thiazolinyl, (C 2-C 6) haloalkenyl group, (C 2-C 6) alkenyl carbonyl, (C 2-C 6) haloalkenyl group carbonyl, (C 2-C 6) alkene oxygen base, (C 2-C 6) haloalkene oxygen base, (C 2-C 6) allyloxycarbonyl, (C 2-C 6) the halo allyloxycarbonyl;
-(C 2-C 6) alkynyl, (C 2-C 6) halo alkynyl, (C 2-C 6) alkynyl carbonyl, (C 2-C 6) halo alkynyl carbonyl, (C 2-C 6) alkynyloxy group, (C 2-C 6) halo alkynyloxy group, (C 2-C 6) alkynyloxy group carbonyl, (C 2-C 6) halo alkynyloxy group carbonyl;
-three (C 1-C 6) alkyl silyl-(C 2-C 6) alkynyl, two (C 1-C 6) alkyl silyl-(C 2-C 6) alkynyl, list (C 1-C 6) alkyl silyl-(C 2-C 6) alkynyl, phenyl silyl-(C 2-C 6) alkynyl;
-(C 6-C 14) aryl, (C 6-C 14) aryloxy, (C 6-C 14) aryl carbonyl and (C 6-C 14) aryloxycarbonyl, its aryl moiety separately can be by halogen, (C 1-C 6) alkyl and/or (C 1-C 6) the haloalkyl replacement;
-(C 6-C 14) aryl-(C 1-C 6) alkyl, (C 6-C 14) aryl-(C 1-C 6) alkoxyl group, (C 6-C 14) aryl-(C 1-C 6) alkyl-carbonyl, (C 6-C 14) aryl-(C 1-C 6) alkyl-carbonyl oxygen base, (C 6-C 14) aryl-(C 1-C 6) alkoxy carbonyl, (C 6-C 14) aryl-(C 1-C 6) alkoxy-carbonyl oxy;
-single ((C 1-C 6) alkyl) amino, single ((C 1-C 6) haloalkyl) amino, two ((C 1-C 6) alkyl) amino, two ((C 1-C 6) haloalkyl) amino, ((C 1-C 6) alkyl-(C 1-C 6) haloalkyl) amino, N-((C 1-C 6) alkyloyl) amino, N-((C 1-C 6) the haloalkane acyl group) amino, aminocarboxyl-(C 1-C 6) alkyl, two (C 1-C 6) alkyl amino-carbonyl-(C 1-C 6) alkyl;
-single ((C 1-C 6) alkyl) aminocarboxyl, list ((C 1-C 6) haloalkyl) aminocarboxyl, two ((C 1-C 6) alkyl) aminocarboxyl, two ((C 1-C 6) haloalkyl) aminocarboxyl, ((C 1-C 6) alkyl-(C 1-C 6) haloalkyl) aminocarboxyl, N-((C 1-C 6) alkyloyl) aminocarboxyl, N-((C 1-C 6) the haloalkane acyl group) aminocarboxyl;
-(C 1-C 6) alkoxyl group-(C 1-C 6) alkyl, (C 1-C 6) alkoxyl group-(C 1-C 6) alkoxyl group, (C 1-C 6) alkoxy carbonyl-(C 1-C 6) alkoxyl group;
-(C 3-C 8) cycloalkyl, its group of naphthene base can be by (C 1-C 6) alkyl and/or the optional replacement of halogen; (C 3-C 8) cycloalkyloxy, (C 3-C 8) cycloalkyl-(C 1-C 6) alkyl, (C 3-C 8) cycloalkyl-(C 1-C 6) haloalkyl, (C 3-C 8) cycloalkyl-(C 1-C 6) alkoxyl group, (C 3-C 8) cycloalkyl-(C 1-C 6) halogenated alkoxy, (C 3-C 8) naphthene base carbonyl, (C 3-C 8) cyclo alkoxy carbonyl, (C 3-C 8) cycloalkyl-(C 1-C 6) alkyl-carbonyl, (C 3-C 8) cycloalkyl-(C 1-C 6) halogenated alkyl carbonyl, (C 3-C 8) cycloalkyl-(C 1-C 6) alkoxy carbonyl, (C 3-C 8) cycloalkyl-(C 1-C 6) halo alkoxy carbonyl, (C 3-C 8) naphthene base carbonyl oxygen base, (C 3-C 8) cyclo alkoxy carbonyl oxygen base, (C 3-C 8) cycloalkyl-(C 1-C 6) alkyl-carbonyl oxygen base, (C 3-C 8) cycloalkyl-(C 1-C 6) halogenated alkyl carbonyl oxygen base, (C 3-C 8) cycloalkyl-(C 1-C 6) alkoxy-carbonyl oxy, (C 3-C 8) cycloalkyl-(C 1-C 6) halo alkoxy carbonyl oxygen base;
-(C 3-C 8) cycloalkenyl group, (C 3-C 8) cyclenes oxygen base, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) haloalkyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkoxyl group, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halogenated alkoxy, (C 3-C 8) cycloalkenyl carbonyl, (C 3-C 8) ring allyloxycarbonyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkyl-carbonyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halogenated alkyl carbonyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkoxy carbonyl, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halo alkoxy carbonyl, (C 3-C 8) cycloalkenyl carbonyl oxygen base, (C 3-C 8) cyclenes oxygen base ketonic oxygen base, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkyl-carbonyl oxygen base, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halogenated alkyl carbonyl oxygen base, (C 3-C 8) cycloalkenyl group-(C 1-C 6) alkoxy-carbonyl oxy, (C 3-C 8) cycloalkenyl group-(C 1-C 6) halo alkoxy carbonyl oxygen base;
-hydroxyl-(C 1-C 6) alkyl, hydroxyl-(C 1-C 6) alkoxyl group, cyano group-(C 1-C 6) alkoxyl group, cyano group-(C 1-C 6) alkyl;
-(C 1-C 6) alkyl sulphonyl, (C 1-C 6) alkylthio, (C 1-C 6) alkyl sulphinyl, (C 1-C 6) halogenated alkyl sulfonyl, (C 1-C 6) halogenated alkylthio, (C 1-C 6) haloalkyl sulfinyl, (C 1-C 6) alkyl sulphonyl-(C 1-C 6) alkyl, (C 1-C 6) alkylthio-(C 1-C 6) alkyl, (C 1-C 6) alkyl sulphinyl-(C 1-C 6) alkyl, (C 1-C 6) halogenated alkyl sulfonyl-(C 1-C 6) alkyl, (C 1-C 6) halogenated alkylthio-(C 1-C 6) alkyl, (C 1-C 6) haloalkyl sulfinyl-(C 1-C 6) alkyl, (C 1-C 6) alkyl sulphonyl-(C 1-C 6) haloalkyl, (C 1-C 6) alkylthio-(C 1-C 6) haloalkyl, (C 1-C 6) alkyl sulphinyl-(C 1-C 6) haloalkyl, (C 1-C 6) halogenated alkyl sulfonyl-(C 1-C 6) haloalkyl, (C 1-C 6) halogenated alkylthio-(C 1-C 6) haloalkyl, (C 1-C 6) haloalkyl sulfinyl-(C 1-C 6) haloalkyl, (C 1-C 6) alkylsulfonyloxy, (C 1-C 6) haloalkyl sulfonyloxy, (C 1-C 6) alkylthio carbonyl, (C 1-C 6) halogenated alkylthio carbonyl, (C 1-C 6) alkylthio ketonic oxygen base, (C 1-C 6) halogenated alkylthio ketonic oxygen base, (C 1-C 6) alkylthio-(C 1-C 6) alkyl, (C 1-C 6) alkylthio-(C 1-C 6) alkoxyl group, (C 1-C 6) alkylthio-(C 1-C 6) alkyl-carbonyl, (C 1-C 6) alkylthio-(C 1-C 6) alkyl-carbonyl oxygen base, (C 4-C 14) aryl sulfonyl, (C 6-C 14) arylthio, (C 6-C 14) aryl sulfonyl kia, (C 3-C 8) cycloalkylthio, (C 3-C 8) alkenylthio group, (C 3-C 8) cyclenes sulfenyl, (C 3-C 6) the alkynes sulfenyl;
-radicals R 1And R 2Form (a C that can contain one or more oxygen and/or sulphur atom together 2-C 6) alkylidene group, wherein said (C 2-C 6) alkylidene group can be replaced by the halogen list or polysubstituted, and each halogenic substituent can be identical or different;
R 3Be selected from hydrogen, (C 1-C 6) alkyl and (C 1-C 6) haloalkyl;
R 4And R 5Be selected from hydrogen, (C independently of one another separately 1-C 6) alkyl, (C 1-C 6) haloalkyl, hydroxyl, (C 1-C 6) alkoxyl group and (C 1-C 6) halogenated alkoxy; Or form 3 to 7 yuan of rings with the carbon atom of their institute's bondings;
R 6And R 7Be selected from hydrogen, (C independently of one another separately 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 1-C 6) alkoxyl group, (C 1-C 6) halogenated alkoxy, (C 6-C 14) aryl, (C 6-C 14) aryloxy, (C 6-C 14) aryl carbonyl and (C 6-C 14) aryloxycarbonyl; Or radicals R 6And R 7Form (a C that can contain one or more oxygen and/or sulphur atom together 2-C 7) alkylidene group, wherein said (C 2-C 7) alkylidene group can be replaced by the halogen list or polysubstituted, and each halogenic substituent can be identical or different,
R 8, R 9, R 10And R 11Be selected from hydrogen, halogen, cyano group, nitro, (C independently of one another separately 1-C 6) alkyl, (C 1-C 6) alkyl-carbonyl, (C 1-C 6) alkoxy carbonyl, (C 1-C 6) alkyl amino-carbonyl, (C 1-C 6) dialkylamino carbonyl, (C 1-C 6) haloalkyl, (C 1-C 6) alkoxyl group, (C 1-C 6) halogenated alkoxy, (C 2-C 6) alkynyl, (C 2-C 6) halo alkynyl, (C 2-C 6) alkynyl carbonyl, (C 2-C 6) halo alkynyl carbonyl, (C 2-C 6) alkynyloxy group, (C 2-C 6) halo alkynyloxy group, (C 2-C 6) alkynyloxy group carbonyl and (C 2-C 6) halo alkynyloxy group carbonyl;
And
X is a key, CH 2, O, S, carbonyl, NH, CR 12R 13And NR 14,
R 12And R 13Be selected from hydrogen, (C independently of one another separately 1-C 6) alkyl and (C 1-C 6) haloalkyl,
R 14Be selected from hydrogen, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl,
A) condition is if R 2Be CF 3, R then 1, R 4, R 5, R 6, R 7, R 8, R 9, R 10Or R 11In at least one group be not hydrogen,
B) if R 1Be NH 2, R then 2Be not chlorine.
2. the formula of claim 1 (I) compound, wherein said radicals R 1Be selected from hydrogen, halogen, cyano group, C (=O) NH 2, NO 2, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 3-C 6) cyclopropyl, (C 1-C 6) alkoxyl group, (C 1-C 6) alkylthio, (C 1-C 6) alkylthio, (C 2-C 6) alkynyl, list (C 1-C 6) alkylamino, two (C 1-C 6) alkylamino and three (C 1-C 6) alkyl silyl-(C 2-C 6) alkynyl.
3. claim 1 or 2 formula (I) compound, wherein said radicals R 2Be selected from hydrogen, halogen, (C 1-C 6) alkyl phenyl, (C 6-C 14) aryl, its aryl can be by (C 1-C 6) alkyl, (C 6-C 14) haloalkyl and/or halogen replacement; C 6Aryl-(C 1-C 6) haloalkyl, (C 1-C 6) alkyl, (C 1-C 6) haloalkyl, (C 1-C 6) alkoxyl group, (C 1-C 6) alkoxyl group-(C 1-C 6) alkyl, (C 3-C 6) cycloalkyl, its group of naphthene base can be by (C 1-C 6) alkyl, (C 6-C 14) halogenated aryl and/or halogen replacement; 1-(C 1-C 6) alkyl cyclopropyl, 1-((C 1-C 6) alkyl-C 6Aryl) cyclopropyl, 1-(phenyl-monohalide base) cyclopropyl, 1-(dihalogenated phenyl) cyclopropyl, list (C 1-C 6) alkylamino, two (C 1-C 6) alkylamino, (C 1-C 6) alkylthio, (C 1-C 6) alkylthio, (C 1-C 6) alkoxyl group and amino.
4. the formula of claim 1 (I) compound, wherein R 1And R 2Carbon atom with their institute's bondings forms one 5 yuan or 6 yuan of rings, and this ring can be selected from 1 or 2 heteroatomss intervals of oxygen and sulphur.
5. each formula (I) compound in the claim 1 to 4, wherein said radicals R 3Be hydrogen or (C 1-C 6) alkyl.
6. each formula (I) compound, wherein radicals R in the claim 1 to 5 4And R 5Be selected from hydrogen, (C independently of one another separately 1-C 6) alkyl, hydroxyl, cyclopropyl and (C 1-C 6) alkoxyl group.
7. each formula (I) compound, wherein radicals R in the claim 1 to 5 4And R 5Form (a C that can contain one or more oxygen and/or sulphur atom together 1-C 7) alkylidene group, wherein said (C 1-C 7) alkylidene group can be replaced by the halogen list or polysubstituted, and each halogenic substituent can be identical or different.
8. each formula (I) compound, wherein radicals R in the claim 1 to 7 6And R 7Be independently from each other hydrogen, (C 1-C 6) alkyl and (C 6-C 14) aryl.
9. each formula (I) compound in the claim 1 to 8, wherein said radicals R 8Be selected from hydrogen, (C 1-C 6) alkyl and halogen.
10. each formula (I) compound in the claim 1 to 9, wherein said radicals R 9Be preferably selected from hydrogen and (C 1-C 6) alkyl.
11. each formula (I) compound in the claim 1 to 10, wherein said radicals R 10Be selected from hydrogen, (C 1-C 6) alkyl, two (C 1-C 6) alkylamino, halogen, (C 2-C 6) thiazolinyl, (C 2-C 6) alkynyl, (C 1-C 6) alkyl-(C 2-C 6) alkynyl, (C 1-C 6) alkoxyl group-(C 1-C 6) alkyl-(C 2-C 6) alkynyl, cyano group, (C 1-C 6) alkoxy carbonyl and aminocarboxyl.
12. each formula (I) compound, wherein R in the claim 1 to 11 11Be selected from hydrogen and (C 1-C 6) alkyl.
13. each formula (I) compound in the claim 1 to 12, wherein X is selected from CH 2, O and a chemical bond.
14. the method for a preparation formula (I) compound,
Figure FPA00001392541100061
Radicals R wherein 1To R 11And X has in the claim 1 to 13 each implication, and this method comprises
(1) amine or its acid salt of formula (II) compound and a kind of formula (III) are reacted,
Figure FPA00001392541100062
R wherein 1And R 2The implication that has in the claim 1 to 11 each, and Z 1Be a commutative group or a leavings group, for example particularly chlorine, trichloromethyl, (C 1-C 4) alkyl sulphonyl, unsubstituted or phenyl-(C of replacing 1-C 4) alkyl sulphonyl or (C 1-C 4) the alkyl phenyl alkylsulfonyl,
15. weeding or plant growth regualting composition, it contains in one or more claims 1 to 13 each formula (I) compound or its salt.
16. a method of preventing and treating noxious plant or coordinate plant growth, this method comprise each formula (I) compound or its salt in one or more claims 1 to 13 of significant quantity is applied to plant, plant parts, plant seed or cultural area.
17. each formula (I) compound or its salt is as the purposes of weedicide or plant-growth regulator in the claim 1 to 13.
18. the purposes of claim 17, wherein said formula (I) compound or its salt are used in useful plants or ornamental plant crop control noxious plant or coordinate plant growth.
19. the purposes of claim 18, wherein said crop plants are the genetically modified crops plant.
20. the purposes of claim 18 or 19, wherein said crop plants is selected from kind of a plant.
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